Substituted 5-aminopyrazoles

ABSTRACT

Substituted 5-aminopyrazoles I ##STR1## where R 1  is C 1  -C 8  -alkyl, C 1  -C 8  -hydroxyalkyl, phenyl which may carry 1-3 of the following radicals: halogen, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or --NR 6  R 7 , and which may additionally carry a number of halogen atoms so that the total number of radicals is 5, R 6  and R 7  are each H or C 1  -C 4  -alkyl, R 2  is H, C 1  -C 4  -alkyl or C 1  -C 4  -haloalkyl, R 3  is CN, --CO--R 8  or --CS--R 8 , R 8  is OH, C 1  -C 4  -alkoxy, NH 2 , C 1  -C 4  -alkylamino or di-C 1  -C 4  -alkylamino, R 4  and R 5  are each H, C 1  -C 4  -alkyl, PX(OR 9 ) 2 , --SO 2  --R 9 , --CX--R 10 , --CX--NH--CY--R 9  or CX--NH--SO 2  --R 11 , X and Y are each O or S, R 9   is one of the substituents R 1 , R 10  is C 1  -C 20  -alkyl, C 1  -C 4  -alkoxy, unsubstituted or substituted phenyl or unsubstituted or substituted NH 2 , R 11  is NH 2 , C 1  -C 4  -alkylamino, di-C 1  -C 4  -alkylamino, pyrrolidinyl, piperidinyl or morpholinyl, R 4  and R 5  together form a group ═CR 12  R 13  or --CO--W--CO--, R 12  is H, NH 2 , C 1  -C 4  -alkylamino or C 3  -C 8  -cycloalkylamino, R 13  is NH 2 , C 1  -C 4  -alkylamino, di-C 1  -C 4  -alkylamino, C 3  -C 8  -cycloalkylamino, pyrrolidin-1-yl, piperidin-1-yl, morpholin-4-yl, unsubstituted or substituted phenyl or unsubstituted or substituted pyridyl and W is an unsubstituted or substituted ethylene or ethenylene bridge, an unsubstituted or substituted 5-membered or 6-membered 1,2-C-bonded aromatic or heteroaromatic bridge, or an unsubstituted or substituted 5-membered or 6-membered 1,2-C-bonded cycloalkylene or cycloalkenylene bridge, 
     and the basic salts of the compounds I in which R 3  is hydroxycarbonyl or hydroxythiocarbonyl, and the acidic salts of the compounds I which contain a basic nitrogen atom, 
     with the exception of 1-phenyl- and 1-methyl-4-cyano-5-acylaminopyrazole, 1-methyl-4-cyano-5-(chloromethylcarbonylamino)-pyrazole, 1-methyl-4-cyano-5-(phenylcarbonylamino)-pyrazole, 1-methyl-4-cyano-5-(p-chlorophenylcarbonylamino)-pyrazole and the compounds I in which R 1  is methyl, phenyl, 4-chlorophenyl or 4-nitrophenyl, R 2  is hydrogen, methyl or trifluoromethyl, R 3  is cyano and R 4  and R 5  are simultaneously hydrogen, and herbicides which contain 2-(4-hetaryloxy)- and 2-(4-aryloxy)-phenoxyacetic acid or -propionic acid derivatives and/or cyclohexenone derivatives as herbicidal active ingredients and substituted 5-aminopyrazoles I&#39; or, in the case of acidic terminal groups or basic nitrogen atoms, the salts of I&#39; as antidotes.

The present invention relates to novel 5-aminopyrazoles of the generalformula I ##STR2## where R¹ is C₁ -C₈ -alkyl, C₁ -C₈ -hydroxyalkyl maycarry or a phenyl group which may carry from one to three of thefollowing radicals: halogen, nitro, C₁ -C₄ -alkyl, partially orcompletely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, partially orcompletely halogenated C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio or --NR⁶ R⁷,where R⁶ and R⁷ are each hydrogen or C₁ -C₄ -alkyl, and the phenyl groupmay additionally carry a further number of halogen atoms so that thetotal number of radicals is 4 or 5;

R² is hydrogen or C₁ -C₄ -alkyl which may be unsubstituted or partiallyor completely halogenated;

R³ is cyano, CO--R⁵ or CS--R⁶, where R⁸ is hydroxyl, C₁ -C₄ -alkoxy,amino, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino;

R⁴ and R⁵ are each hydrogen, C₁ -C₄ -alkyl, PX(OR⁵)₂, SO₂ --R⁹, CX--R¹⁰,CX--NH--CY--R⁹ or CX--NH--SO₂ --R¹¹, where

X and Y are each oxygen or sulfur;

R⁹ is one of the substituents R¹ ;

R¹⁰ is C₁ -C₂₀ -alkyl, C₁ -C₄ -alkoxy or a phenyl group which may carryfrom one to three of the following radicals: halogen, nitro, C₁ -C₄-alkyl, partially or completely halogenated C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, partially or completely halogenated C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio or --NR⁶ R⁷, and which may additionally carry a furthernumber of halogen atoms so that the total number of radicals is 5; aminowhich may be unsubstituted or may carry a C₁ -C₄ -alkyl, cycloalkyl orphenyl radical, where the phenyl radical in turn may carry from one tothree of the following radicals: halogen, C₁ -C₄ -alkyl, partially orcompletely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, partially orcompletely halogenated C₁ -C₄ -alkoxy or C₁ -C₄ -alkylthio and thephenyl group may additionally contain a further number of halogen atomsso that the total number of radicals is 4 or 5;

R¹¹ is amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, pyrrolidinyl,piperidinyl or morpholinyl;

or

R⁴ and R⁵ together form a group ═CR¹² R¹³ or --CO--W--CO--, where R¹² ishydrogen, amino, C₁ -C₄ -alkylamino or C₃ -C₈ -cycloalkylamino;

R¹³ is amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₃ -C₈-cycloalkylamino, pyrrolidin-1-yl, piperidin-1-yl, morpholin-4-yl,phenyl or pyridyl, where the two last-mentioned substituents mayfurthermore carry from one to three of the following radicals: halogen,nitro, C₁ -C₄ -alkyl, partially or completely halogenated C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy, partially or completely halogenated C₁ -C₄ -alkoxy or C₁-C₄ -alkylthio;

W is an ethylene or ethenylene bridge, a 5-membered or 6-membered1,2-C-bonded aromatic or heteroaromatic bridge having a nitrogen, oxygenor sulfur atom as hetero atom, where these bridge members mayfurthermore carry, on each substitutable carbon atom, a radical selectedfrom up to 2 of the following: halogen, C₁ -C₄ -alkyl, partially orcompletely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, partially orcompletely halogenated C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio and partiallyor completely halogenated C₁ -C₄ -alkylthio, and where the bridgemembers may additionally carry a number of halogen atoms equivalent tothe number of further substitutable carbon atoms, or

a 5-membered or 6-membered 1,2-C-bonded cycloalkylene or cycloalkenylenebridge, where these substituents may furthermore carry from one to fourof the following radicals: halogen or C₁ -C₄ -alkyl;

and the basic salts of the compounds I in which R³ is hydroxycarbonyl orhydroxythiocarbonyl and the acidic salts of the compounds I whichcontain a basic nitrogen atom,

with the exception of 1-phenyl- and1-methyl-4-cyano-5-acylaminopyrazole,1-methyl-4-cyano-5-(chloromethylcarbonylamino)-pyrazole,1-methyl-4-cyano-5-(phenylcarbonylamino)-pyrazole,1-methyl-4-cyano-5-(p-chlorophenylcarbonylamino)-pyrazole, and thecompounds I in which R¹ was methyl, phenyl, 4-chlorophenyl or4-nitrophenyl, R² was hydrogen, methyl or trifluoromethyl, R³ was cyanoand R⁴ and R⁵ were simultaneously hydrogen.

The present invention furthermore relates to a process for thepreparation of the compounds I and to herbicides containing one or moreherbicidal active ingredients from the group consisting of

A) the 2-(4-hetaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivativesof the formula X ##STR3## where R^(a) is phenyl, pyridyl, benzoxazyl,benzothiazyl or benzopyrazinyl, where these aromatic ring systems maycarry up to two of the following radicals: halogen, nitro, C₁ -C₄-alkyl, partially or completely halogenated C₁ -C₄ -alkyl and/orpartially or completely halogenated C₁ -C₄ -alkoxy; R^(b) is hydrogen,C₁ -C₅ -alkyl, C₃ -C₅ -alkylideneimino, C₃ -C₅ -alkylideneiminooxy-C₂ -or C₃ -alkyl or one equivalent of a plant-tolerated cation and

R^(c) is hydrogen or methyl,

and

B) the cyclohexenone derivates of the formula XI ##STR4## where R^(d) isC₁ -C₄ -alkyl;

R^(e) is C₁ -C₄ -alkyl, C₃ - or C₄ -alkenyl, C₃ - or C₄ -alkynyl orpartially or completely halogenated C₃ - or C₄ -alkenyl;

a C₁ -C₄ -alkylene or C₂ -C₄ -alkenyl chain, both of which mayfurthermore carry from one to 3 C₁ -C₃ -alkyl radicals and/or halogenatoms, or a 3-membered to 6-membered alkylene or 4-membered to6-membered alkenylene chain which may be substituted by C₁ -C₃ -alkyland each of which contains as a chain member an oxygen or sulfur atomnot directly adjacent to the oxime ether moiety, all the abovementionedchains carrying on the terminal position the phenyl ring which in turnmay be substituted by from one to three radicals selected from the groupconsisting of one benzyloxycarbonyl or phenyl radical and from one tothree of the following radicals: nitro, cyano, halogen, C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, partially or completely halogenatedC₁ -C₄ -alkyl, partially or completely halogenated C₁ -C₄ -alkoxy,carboxyl and C₁ -C₄ -alkoxycarbonyl, and it being possible for thephenyl ring furthermore to carry a number of halogen atoms such that thetotal number of radicals is 4 or 5;

thienylmethyl which may furthermore carry a halogen atom;

R^(f) is C₁ -C₄ -alkyl which may be monosubstituted by C₁ -C₄ -alkylthioor by C₁ -C₄ -alkoxy;

a 5-membered or 6-membered saturated or monounsaturated ring systemwhich, in addition to carbon members, may contain an oxygen or sulfuratom or a sulfinyl or sulfonyl group, where this ring may carry up tothree of the following radicals: hydroxyl, halogen, C₁ -C₄ -alkyl,partially or completely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy and/orC₁ -C₄ -alkylthio;

a 10-membered saturated or monounsaturated heterocyclic structure whichcontains two oxygen atoms or sulfur atoms and may be substituted by upto three C₁ -C₄ -alkyl groups and/or methoxy groups;

phenyl or pyridyl, where these groups may carry up to three of thefollowing radicals: C₁ -C₄ -alkyl, partially or completely halogenatedC₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -alkenyloxy, C₃-C₆ -alkynyloxy, C₁ -C₄ -alkoxy-C₁ -C₃ -alkyl, C₁ -C₄ -dialkoxy-C₁ -C₃-alkyl, formyl, halogen and/or benzoylamino;

pyrrolyl, pyrazolyl, thiazolyl or isoxazolyl, each of which may carry aC₁ -C₄ -alkyl group;

R^(g) is hydrogen or hydroxyl or, when R^(f) is C₁ -C₆ -alkyl, is C₁ -C₆-alkyl;

R^(h) is hydrogen, cyano, halogen, C₁ -C₄ -alkoxycarbonyl or a group##STR5## R^(i) is hydrogen or one equivalent of an environmentallycompatible cation,

and one or more antagonistic substituted 5-aminopyrazoles of the formulaI', where I' has the same meaning as I without the exception, or a basicsalt of the compounds I' in which R³ is hydroxycarbonyl orhydroxythiocarbonyl, or an acidic salt of the compounds I' which carry abasic nitrogen atom.

The present invention furthermore relates to methods for selectivelycontrolling undesirable plant growth with these herbicides.

Aust. J. Chem. 42 (1989), 747 discloses 1-methyl- and1-phenyl-substituted 5-amino-4-cyanopyrazoles, and J. Org. Chem. 21(1956), 1240 discloses 1-alkyl- and 1-aryl-substituted5-amino-4-cyanopyrazoles and 1-alkyl- and 1-aryl-substituted5-amino-4-pyrazolecarboxamides of the same type as the compounds I.

5-Amino-4-pyrazolecarboxamides of the same type as compounds I, havingdifferent radicals in the 1- and/or 3-positions, are described in J.Heterocycl. Chem. 12 (1975), 1199.

The compounds known from the literature serve as intermediates.

Furthermore, Bull. Chem. Soc. Jpn. 60 (1987), 4480 discloses5-amino-4-cyano-1-phenyl-3-trifluoromethylpyrazole and5-amino-4-cyano-1-(p-nitrophenyl)-3-trifluoromethylpyrazole asbyproducts.

According to EP-A 201 852, EP-A 235 628 and EP-A 392 241,5-amino-1-arylpyrazoles which carry an alkylthio, alkylsulfinyl oralkylsulfonyl radical in the 4-position have insecticidal, acaricidaland nematicidal activity.

Finally, EP-A 418 845 discloses pharmaceutically active1-(het)arylpyrazoles which by definition may carry, inter alia, analkylamino group.

An antidote effect of the known 5-aminopyrazoles in combination withherbicidal active ingredients is not mentioned in the statedpublications.

It was an object of the present invention to provide compounds which,when the abovementioned herbicides of the formulae X and XI are used,reduce disadvantages at least to such an extent that the yield of thecrops at harvest is no longer reduced or not reduced significantly.

We have found that this object is achieved by the substituted5-aminopyrazoles I defined at the outset.

We have also found processes for the preparation of the compounds I andmethods for the combined treatment of crops on the one hand with theantidote compounds I or I', where I' has the same meaning as I withoutthe exception, and, on the other hand, with the herbicides X and/or XI,whether the herbicidal active ingredient and the antidote compound areformulated and applied together or separately and, in the case ofseparate application, the order in which the herbicidal activeingredient and the antidote are applied being unimportant.

Derivatives I and I' having acidic terminal groups or having basicnitrogen atoms may be in the form of their agriculturally useful salts.

Suitable acid addition salts are the salts of acids which do notadversely affect the antidote activity of I, for example thehydrochlorides, hydrobromides, sulfates, nitrates, phosphates, oxalatesor dodecylbenzenesulfonates.

Suitable basic salts are the salts of bases which do not adverselyaffect the antidote activity of I, for example the alkali metal salts,in particular the sodium and potassium salts, the alkaline earth metalsalts, in particular calcium, magnesium and barium salts, transitionmetal salts, in particular manganese, copper, zinc and iron salts,ammonium salts which may carry from one to three C₁ -C₄ -alkyl orhydroxy-C₁ -C₄ -alkyl substituents and/or a phenyl or benzylsubstituent, in particular diisopropylammonium, tetramethylammonium,tetrabutylammonium, trimethylbenzylammonium andtrimethyl-(2-hydroxyethyl)-ammonium salts, the phosphonium salts, thesulfonium salts, in particular tri-C₁ -C₄ -alkylsulfonium salts, and thesulfoxonium salts, in particular tri-C₁ -C₄ -alkylsulfoxonium salts.

The substituents in the novel compounds I have the following specificmeanings:

R¹ is branched or straight-chain C₁ -C₈ -alkyl, in particular C₁ -C₄-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl ortert-butyl, particularly preferably methyl;

C₁ -C₈ -hydroxyalkyl, in particular C₁ -C₄ -hydroxyalkyl, such ashydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl;

phenyl which may furthermore carry from one to three of the followingradicals:

halogen, such as fluorine, chlorine, bromine or iodine, in particularfluorine or chlorine, nitro,

C₁ -C₄ -alkyl as stated above, partially or completely halogenated C₁-C₄ -alkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl,chloromethyl, trichloromethyl, bromomethyl, pentafluoroethyl or2-chloro-1,1,2-trifluoroethyl,

C₁ -C₄ -alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxyor tert-butoxy,

partially or completely halogenated C₁ -C₄ -alkoxy, such asfluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy,dichloromethoxy or trichloromethoxy,

C₁ -C₄ -alkylthio, such as methylthio, ethylthio, n-propylthio,isopropylthio, n-butylthio or tert-butylthio, preferably methylthio orethylthio, or

--NR₆ R⁷, where R⁶ and R⁷ are each hydrogen or C₁ -C₄ -alkyl as statedabove,

and where the phenyl group may additionally contain a number of halogenatoms so that the total number of radicals is 4 or 5,

particularly preferably phenyl or 4-chlorophenyl;

R¹ is very particularly preferably methyl or phenyl;

R² is hydrogen;

C₁ -C₄ -alkyl as stated above;

partially or completely halogenated C₁ -C₄ -alkyl as stated above;

R² is particularly preferably hydrogen;

R³ is cyano;

CO--R⁸ or CS--R⁸, where R⁸ is hydroxyl, C₁ -C₄ -alkoxy as stated above,in particular methoxy or ethoxy, amino, C₁ -C₄ -alkylamino, such asmethylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino ortert-butylamino, in particular methylamino or ethylamino, or di-C₁ -C₄-alkylamino, such as dimethylamino, diethylamino, methylethylamino, ormethyl-n-butylamino;

R³ is very particularly preferably cyano;

R⁴ and R⁵ are each hydrogen;

C₁ -C₄ -alkyl as stated above;

PX(OR⁹)₂, SO₂ --R⁹, CX--R¹⁰, CX--NH--CY--R⁹ or CX--NH--SO₂ --R¹, where Xand Y are each oxygen or sulfur;

R⁹ is one of the substituents R¹ ;

R¹⁰ is branched or straight-chain C₁ -C₂₀ -alkyl, in particular C₁ -C₆-alkyl as stated above, C₁ -C₄ -alkoxy as stated above,

phenyl which may furthermore carry from one to three of the followingradicals: halogen as stated above, in particular fluorine or chlorine,nitro,

C₁ -C₄ -alkyl as stated above, in particular methyl, partially orcompletely halogenated C₁ -C₄ -alkyl as stated above, in particulartrifluoromethyl,

C₁ -C₄ -alkoxy as stated above, in particular methoxy, partially orcompletely halogenated C₁ -C₄ -alkoxy as stated above, in particularmethoxy or ethoxy,

C₁ -C₄ -alkylthio as stated above, in particular methylthio, or --NR⁶ R⁷as stated above,

and the phenyl group may additionally carry a number of halogen atoms asstated above, in particular fluorine or chlorine, so that the totalnumber of radicals is 4 or 5;

amino which may be unsubstituted or may carry a C₁ -C₄ -alkyl radical asstated above, in particular methyl or ethyl, a C₃ -C₈ -cycloalkylradical, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl or cyclooctyl, in particular cyclopropyl, cyclopentyl orcyclohexyl, or a phenyl radical, which in turn may carry from one tothree of the following radicals: halogen as stated above, in particularfluorine or chlorine, C₁ -C₄ -alkyl as stated above, partially orcompletely halogenated C₁ -C₄ -alkyl as stated above, in particulartrifluoromethyl or trichloromethyl, C₁ -C₄ -alkoxy as stated above, inparticular methoxy or ethoxy, partially or completely halogenated C₁ -C₄-alkoxy as stated above, in particular trifluoromethoxy ortrichloromethoxy, or C₁ -C₄ -alkylthio as stated above, in particularmethylthio or ethylthio, and the phenyl radical may additionally carry anumber of halogen atoms as stated above, in particular fluorine orchlorine so that the total number of radicals is 4 or 5;

R¹¹ is amino,

C₁ -C₄ -alkylamino as stated above, in particular methylamino orethylamino,

di-C₁ -C₄ -alkylamino as stated above, in particular dimethylamino ordiethylamino,

pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl or morpholin-4-yl, wherethe heterocyclic radicals may carry one or two C₁ -C₄ -alkyl groups asstated above;

or R⁴ and R⁵ together form a group ═CR¹² R¹³ or --CO--W--CO--,

where

R¹² is hydrogen, amino,

C₁ -C₄ -alkylamino as as stated above, in particular methylamino orethylamino,

C₃ -C₈ -cycloalkylamino, such as cyclopropylamino, cyclobutylamino,cyclopentylamino, cyclohexylamino, cycloheptylamino or cyclooctylamino,in particular cyclopropylamino, cyclopentylamino or cyclohexylamino;

R¹³ is hydrogen, amino,

C₁ -C₄ -alkylamino as stated above, in particular methylamino orethylamino,

di-C₁ -C₄ -alkylamino as stated above, in particular dimethylamino ordiethylamino,

C₃ -C₈ -cycloalkylamino as stated above, in particular cyclopropylamino,cyclopentylamino or cyclohexylamino;

pyrrolidin-1-yl, piperidin-1-yl, morpholin-4-yl, phenyl or pyridyl,where the two last-mentioned substituents may carry from one to three ofthe following radicals: halogen as stated above, in particular fluorineor chlorine, nitro, C₁ -C₄ -alkyl as stated above, in particular methyl,ethyl, isopropyl or tert-butyl, partially or completely halogenated C₁-C₄ -alkyl as stated above, in particular trifluoromethyl, C₁ -C₄-alkoxy as stated above, in particular methoxy or ethoxy, partially orcompletely halogenated C₁ -C₄ -alkoxy as stated above, in particulartrifluoromethoxy and/or C₁ -C₄ -alkylthio as stated above, in particularmethylthio,

particularly preferably phenyl or pyrid-2-yl;

W is an ethylene or ethenylene bridge, a 5-membered or 6-membered1,2-C-bonded aromatic or heteroaromatic bridge having a nitrogen, oxygenor sulfur atom as the hetero atom, where these bridge members mayfurthermore carry, on each substitutable carbon atom, a radical selectedfrom up to 2 of the following: halogen as stated above, in particularfluorine or chlorine, C₁ -C₄ -alkyl as stated above, in particularmethyl or tert-butyl, partially or completely halogenated C₁ -C₄ -alkylas stated above, in particular trifluoromethyl, C₁ -C₄ -alkoxy as statedabove, in particular methoxy, partially or completely halogenated C₁ -C₄-alkoxy as stated above, in particular trifluoromethoxy, C₁ -C₄-alkylthio as stated above, in particular methylthio and/or partially orcompletely halogenated C₁ -C₄ -alkylthio, such as fluoromethylthio,chloromethylthio, bromomethylthio, trichloromethylthio,trifluoromethylthio or pentafluoroethylthio, in particulartrifluoromethylthio,

and where the bridge members may furthermore carry a number of halogenatoms as stated above, in particular fluorine or chlorine, equivalent tothe number of further substitutable carbon atoms present in the aromaticmoiety,

particularly preferably ##STR6## or a 5-membered or 6-membered1,2-C-bonded cycloalkylene or cycloalkenylene bridge, such ascyclopentylidene, cyclohexylidene, cyclopentenylidene orcyclohexenylidene, where these substituents may furthermore carry fromone to four halogen atoms as stated above, in particular fluorine orchlorine, and/or C₁ -C₄ -alkyl as stated above, in particular methyl,

particularly preferably ##STR7##

The substituted 5-aminopyrazoles of the formula I are obtainable byvarious methods, preferably by one of the following processes:

a) Reaction of alkoxycyanoalkenes II with hydrazines III to give5-aminopyrazoles Ia, where R⁴ and R⁵ are each hydrogen: ##STR8## L is C₁-C₄ -alkoxy.

The reaction is usually carried out in a conventional manner [cf. Robinset al., J. Org. Chem. 21 (1956), 1240] in an inert solvent or diluent,for example in an alcohol, such as methanol, ethanol, n-propanol orisopropanol, in an ether, such as dioxane or tetrahydrofuran, or in apolar aprotic solvent, such as dimethylformamide, dimethyl sulfoxide orN-methylpyrrolidone, or, with the use of a phase transfer catalyst, in a2-phase system of water and a hydrocarbon, eg. carbon tetrachloride.

In the case of compounds having a lower reactivity, it is advisable tocarry out the reaction in the presence of a strong organic or inorganicbase.

Examples of suitable bases are alkali metal hydroxides, such as sodiumhydroxide or potassium hydroxide, alkaline earth metal hydroxides, suchas calcium hydroxide, alkali metal alcoholates, such as sodiummethylate, sodium ethylate, potassium ethylate or potassiumtert-butylate, alkaline earth metal alcoholates, such as calciumalcoholate, alkali metal hydrides, such as sodium hydride or potassiumhydride, alkaline earth metal hydrides, such as calcium hydride,aliphatic amines, such as dimethylamine, triethylamine ortriisopropylamine, dimethylaniline, dimethylbenzylamine, piperidine andheteroaromatic amines, such as pyridine or 4-dimethylaminopyridine.

In the case of the amines, the reaction can also be carried out in anexcess of base in the absence of a solvent.

Examples of suitable phase transfer catalysts are trioctylpropylammoniumchloride and cetyltrimethylammonium chloride [cf. Synthesis (1974),867].

All reactants are advantageously used in stoichiometric amounts, but anexcess of up to about 10 mol % of one or the other component may also beused.

If the base is used as a solvent, it is present in a relatively largeexcess.

In general, the reaction temperature is from 0° to 150° C. C preferablyfrom 20° to 100° C. in particular the boiling point of the particularsolvent.

The reaction is usually carried out at atmospheric pressure or at theautogenous pressure of the solvent used.

Further possible methods of synthesis comprise reacting

acrylonitrile derivatives with arylhydrazines, the open-chain productthen being oxidized with air or sodium hypochlorite and cyclized in thepresence of a base (cf. EP-A 245 646);

acetonitrile derivatives and orthoformic esters with hydrazincs II [cf.Dooley, Aust. J. Chem. 42 (1989), 747]

and

acetonitrile derivatives with hydrazonoyl bromides [cf. Tanaka et al.,Bull. Chem. Soc. Jpn. 60 (1987), 4480].

b) Reaction of substituted 5-aminopyrazoles Ia with an electrophiliccompound IV to IX: ##STR9## Hal is chlorine or bromine.

The reactions are usually carried out by a conventional process in aninert solvent or diluent in the presence of a base:

for the reaction of Ia with carbonyl halides and anhydrides to giveamides and imides, respectively, see Henecka in Houben-Weyl, Methodender Organischen Chemie, Volume 8, pages 653-713;

for the reaction of Ia with sulfonyl chlorides to give sulfonamides, seeMutz in Houben-Weyl, Methoden der Organischen Chemie, Volume 9, pages599-658;

for the reaction of Ia with iso(thio)cyanates to give (thio)ureas, seePetersen in Houben-Weyl, Methoden der Organischen Chemie, Volume 8,pages 129-136;

for the reaction of Ia with aromatic aldehydes to give Schiff bases, seeFreytag in Houben-Weyl, Volume 11/2, pages 73-98.

Examples of suitable solvents are aliphatic hydrocarbons, such asn-hexane, gasoline and petroleum ether, aromatic hydrocarbons, such asbenzene, toluene and o-, m- and p-xylene, chlorohydrocarbons, such asdichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane andchlorobenzene, nitrogen-containing heteroaromatics, such as pyridine andquinoline, cyclic ethers, such as tetrahydrofuran and dioxane, nitriles,such as acetonitrile and propionitrile and dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone, or a mixture of the stated solvents.In the presence of phase transfer catalysts, the reaction can also becarried out in a 2-phase system of water and a hydrocarbon, eg. carbontetrachloride.

Regarding the usable bases, phase transfer catalysts, the amounts andthe pressure, the data given for method (a) are applicable.

In general, the reaction temperature is from 0° to 200° C., preferablyfrom 20° to 140° C. in particular the boiling point of the relevantsolvent.

The electrophilic compounds IV to IX are known or are obtainable byknown processes (cf. Sustmann in Houben-Weyl: Methoden der OrganischenChemie, Volume E5, pages 590-608 and 634-652). The educts VIIa and VIIbare advantageously prepared in situ from halosulfonyl isocyanates andreactive compounds R¹ --H, and the compounds VIIIa and VIIIb areprepared in a similar manner from isocyanate salts, such as ammoniumisocyanate and compounds Hal--CY--R⁹.

The substituted 5-aminopyrazoles I and I' are suitable as antidotes formaking herbicidal active ingredients move compatible with crops such asmillet, rice, corn, cereals (wheat, rye, barley and oats), cotton, sugarbeet, sugar cane and soybean. They have an antagonistic effect onherbicides of a very wide range of classes, such as triazines,phenylurea derivatives, carbamates, thiocarbamates, haloacetanilides,benzoic acid derivatives and in particular halophenoxyacetic esters,substituted phenoxyphenoxyacetic esters, phenoxyphenoxypropionic estersand cyclohexenone derivatives.

Herbicidal active ingredients from the group consisting of the2-(4-hetaryloxy)- or 2-(4-aryloxy)phenoxyacetic acid derivatives of theformula X ##STR10## where R^(a) is phenyl, pyridyl, benzoxazyl,benzothiazyl or benzopyrazinyl, where these aromatic ring systems maycarry up to two of the following radicals: halogen, nitro, C₁ -C₄-alkyl, C₁ -C₄ -haloalkyl and/or C₁ -C₄ -haloalkoxy,

R^(b) is hydrogen, C₁ -C₄ -alkyl or one equivalent of a plant-toleratedcation and

R^(c) is hydrogen or methyl,

are disclosed in the literature, for example in DE-A-22 23 894, DE-A-2433 067, DE-A-25 76 251, DE-A-30 04 770, BE-A-868 875 and BE-A-858 618.

They are used for controlling undesirable plants from the Gramineaefamily. However, the compatibility of these substances with crops variesfrom commercially acceptable to non-tolerated, depending on thesubstituents and application rate.

The same applies to cyclohexenone derivatives of the formula XI##STR11## where R^(d) is C₁ -C₄ -alkyl, such as methyl, ethyl, n-propyl,isopropyl, n-butyl or tert-butyl, preferably ethyl or n-propyl;

R^(e) is C₁ -C₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl,n-butyl or tert-butyl, preferably ethyl or n-propyl, C_(a) - or C₄-alkenyl, preferably prop-2-enyl, C₃ - or C₄ -alkinyl or C₃ - or C₄-haloalkenyl, preferably 3-chloroprop-2-en-1-yl,

a C₁ -C₄ -alkylene or C₂ -C₄ -alkenylene chain, both of which mayfurthermore carry from one to three C₁ -C₃ -alkyl radicals and/orhalogen atoms, or a 3-membered to 6-membered alkylene or 4-membered to6-membered alkenylene chain which may be substituted by C₁ -C₃ -alkyland each of which contains as a chain member an oxygen or sulfur atomnot directly adjacent to the oxime ether moiety, all the abovementionedchains carrying as a terminal group the phenyl ring which in turn may besubstituted by from one to three radicals selected from a groupconsisting of a benzyloxycarbonyl or phenyl radical and from one tothree of each of the following radicals: nitro, cyano, halogen, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, partially or completelyhalogenated C₁ -C₄ -alkyl, partially or completely halogenated C₁ -C₄-alkoxy, carboxyl and C₁ -C₄ -alkoxycarbonyl, and it being possible forthe phenyl ring furthermore to carry a number of halogen atoms such thatthe total number of radicals is 4 or 5; 4-(p-fluorophenyl)-but-3-enyl,4-(p-chlorophenyl)-but-3-enyl and 2-(p-chlorophenoxy)-propyl areparticularly preferred;

thienyl as stated for R^(d), which may carry a halogen atom;

R⁵ is C₁ -C₄ -alkyl which may be monosubstituted or disubstituted by C₁-C₄ -alkylthio or by C₁ -C₄ -alkoxy,

a 5-membered or 6-membered saturated or monounsaturated ring systemwhich, in addition to carbon atoms, may carry an oxygen or sulfur atomor a sulfinyl or sulfonyl group, preferably tetrahydropyranyl,dihydropyranyl and tetrahydrothiopyranyl, where the ring system mayfurthermore carry from one to three radicals selected from the groupconsisting of hydroxyl, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁-C₄ -alkoxy and/or C₁ -C₄ -alkylthio,

a 10-membered saturated or monounsaturated heterocyclic structure whichcontains two non-adjacent oxygen atoms or sulfur atoms and may besubstituted by up to three C₁ -C₄ -alkyl groups and/or methoxy groups,

phenyl, pyridyl, thiazolyl, pyrazolyl, pyrrolyl or isoxazolyl, wherethese groups may each carry from one to three, preferably one or two,radicals selected from the group consisting of: C₁ -C₄ -alkyl, C₁ -C₄-haloalkyl, C₁ -C-alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -alkenyloxy, C₃ -C₆-alkinyloxy, C₁ -C₄ -alkoxy-C₁ -C₃ -alkyl, C₁ -C₄ -dialkoxy-C₁ -C₃-alkyl, formyl, halogen and benzoylamino;

R^(g) is hydrogen or hydroxyl or, when R^(f) is C₁ -C₆ -alkyl, is C₁ -C₆-alkyl, preferably hydrogen;

R^(h) is hydrogen, cyano, halogen, C₁ -C₄ -alkoxycarbonyl or a C₁ -C₄-alkylketoxime group, preferably hydrogen; and

R^(i) is hydrogen or one equivalent of an agriculturally useful cation.

They are likewise described in the literature (for example EP-A 228 598,EP-A 230 235, EP-A 238 021, EP-A 368 227, U.S. Pat. No. 4,432,786, DE-A24 39 104, DE-A 40 14 986 and DE-A 40 33 423) as herbicides and are usedpredominantly for controlling undesirable grasses in dicotyledon cropsand in grasses which do not belong to the Gramineae family. Depending onthe structure of the substituents and the dose used, compounds of thisgroup can also be employed for selectively controlling undesirablegrasses in gramineous crops, such as wheat and rice.

Cyclohexenone derivatives of the formula XI in which R^(e) is anunsubstituted or substituted alkyl or alkenyl, eg. butyl orbutenylphenyl, radical can be prepared in a conventional manner fromknown derivatives of the formula XII (EP-A 80 301, EP-A 125 094, EP-A142 741, U.S. Pat. No. 4,249,937, EP-A 137 174 and EP-A 177 913) and thecorresponding hydroxylamines of the formula XIII (Houben-Weyl, 10/1,page 1181 et seq.) (EP-A 169 521). ##STR12##

The reaction is advantageously carried out in the heterogeneous phase ina solvent at an adequate temperature below about 80° C., in the presenceof a base, and the hydroxylamine XIII is used in the form of itsammonium salt.

Examples of suitable bases are carbonates, bicarbonates, acetates,alcoholates or oxides of alkali or alkaline earth metals, in particularsodium hydroxide, potassium hydroxide, magnesium oxide and calciumoxide. Organic bases, such as pyridine or tertiary amines, can also beused. The base is added, for example, in an amount of from 0.5 to 2 molequivalents, based on the ammonium compound.

Examples of suitable solvents are dimethyl sulfoxide, alcohols, such asmethanol, ethanol and isopropanol, aromatic hydrocarbons, such asbenzene and toluene, chlorohydrocarbons, such as chloroform anddichloroethane, aliphatic hydrocarbons, such as hexane and cyclohexane,esters, such as ethyl acetate, and ethers, such as diethyl ether,dioxane and tetrahydrofuran. The reaction is preferably carried out inmethanol using sodium bicarbonate as the base.

The reaction is complete after a few hours. The target compound can beisolated, for example, by evaporating down the mixture, partitioning theresidue between methylene chloride and water and distilling off thesolvent under reduced pressure.

However, it is also possible directly to use the free hydroxylaminebase, for example in the form of an aqueous solution, for this reaction;a single-phase or two-phase reaction mixture is obtained, depending onthe solvent used for the compound XII.

Examples of suitable solvents for this version are alcohols, such asmethanol, ethanol, isopropanol and cyclohexanol, aliphatic and aromatichydrocarbons and chlorohydrocarbons, such as hexane, cyclohexane,methylene chloride, toluene and dichloroethane, esters, such as ethylacetate, nitriles, such as acetonitrile, and cyclic ethers, such asdioxane and tetrahydrofuran.

Alkali metal salts of the compounds XI can be obtained by treating the3-hydroxy compounds with sodium hydroxide, potassium hydroxide or sodiumor potassium alcoholate in aqueous solution or in an organic solvent,such as methanol, ethanol, acetone or toluene.

Other metal salts, such as manganese, copper, zinc, iron, calcium,magnesium and barium salts, can be prepared from the sodium salts in aconventional manner, as can ammonium and phosphonium salts by means ofammonia or ammonium, phosphonium, sulfonium or sulfoxonium hydroxides.

The compounds of type XII can be prepared, for example, from thecorresponding cyclohexane-1,3-diones of the formula XIV ##STR13## whereZ is hydrogen or methoxycarbonyl and R^(g) is hydrogen, by known methods(Tetrahedron Lett. (1975), 2491).

It is also possible to prepare the compounds of the formula XII via theenol ester intermediates, which are obtained in the reaction ofcompounds of the formula XIV with acid chlorides in the presence of abase and are then subjected to a rearrangement reaction with certainimidazole or pyridine derivatives (Japanese Preliminary PublishedApplication 79/063 052). ##STR14##

The compounds of the formula XIV are obtained by a number of knownprocess steps, starting from known precursors.

The hydroxylamines XIII in which R^(e) is unsubstituted or substitutedphenylbutyl are synthesized according to the following reaction scheme,for example by

a) alkylation of cyclic hydroxyimides XV with suitable phenylbutylhalides and subsequent elimination of the protective group, for examplewith hydrazine or ethanolamine, similarly to Examples from EP-A 244 786or Houben-Weyl, Methoden der organischen Chemie, Volume X/1, page 1152et seq. or

b) hydrogenation of N-4-phenylbutenyloxyphthalimides whose preparationis described in DE-A 38 38 310, by means of suitable catalysts, forexample palladium on active carbon, in suitable inert solvents, such asmethanol, tetrahydrofuran or dioxane, and subsequent elimination of theprotective group as described above.

The hydrogenation is advantageously carried out at from 20° C. to theboiling point of the solvent, in particular at room temperature, by aconventional method, at atmospheric, superatmospheric or reducedpressure. A pressure of from 1 to 10, in particular 1 to 2, bar ispreferred. ##STR15## Ph=unsubstituted or substituted phenyl

Examples of suitable cyclic hydroxyimides XV are the followingsubstances: ##STR16##

The hydroxylamines XIII in which R^(e) is unsubstituted or substitutedbutenylphenyl and the phenyl radical abbreviated below to Ph may in turnbe substituted or unsubstituted are synthesized according to thefollowing reaction scheme by diazotization of aniline derivatives andsubsequent coupling of the diazonium salt to a correspondinglysubstituted butadiene XVI. The resulting mixture of XVIIa and XVIIb iscoupled to a cyclic hydroxyimide XV, and the protected hydroxylaminederivative XVIII obtained is cleaved with 2-aminoethanol to give thefree hydroxylamine XIII: ##STR17##

The radicals R^(j), R^(k) and R^(l) independently of one another areeach hydrogen, C₁ -C₃ -alkyl and/or halogen. Hal is halogen, preferablychlorine or bromine.

The halides XVIIa required for the above synthesis of the hydroxylaminesof the formula XIII can be prepared as a mixture with XVIIb by processesknown from the literature, for example by reacting diazonium salts ofaromatic or heteroaromatic anilines with dienes. The range ofapplication of the reaction is discussed in Organic Reactions 11 (1960),189 or 24 (1976), 225.

Coupling of the isomeric halides XVIa and XVIb to a cyclic hydroxyimideof the formula XV gives exclusively the cyclic imido ethers of theformula XVIII, which, after elimination of the protective group on thenitrogen, give the hydroxylamines XIII.

The reaction with a hydroxyimide XIV (Routes a and c) is carried out inthe presence of an acid acceptor and of a solvent. For cost reasons,hydroxyphthalimide is preferably used as the hydroxyimide XV.

Suitable acid acceptors are alkali metal carbonates, such as potassiumcarbonate or sodium carbonate, alkali metal bicarbonates, such aspotassium bicarbonate or sodium bicarbonate, tertiary amines, such astrimethylamine or triethylamine, and basic heterocycles, such aspyridine. For cost reasons, potassium carbonate and sodium carbonate arepreferred.

Suitable solvents are aprotic dipolar organic solvents, eg.dimethylformamide, dimethyl sulfoxide and/or sulfolane.

Alkylation under phase transfer conditions is also possible. The organicsolvents used here are water-immiscible compounds, such as hydrocarbonsor chlorohydrocarbons. Suitable phase transfer catalysts are quaternaryammonium and phosphonium salts.

The cleavage of the cyclic imido ethers XVIII is carried out similarlyto a process described in EP-A 244 786, using alkanolamines. Thehydroxylamines XIII can be isolated by this process as free bases or assalts after precipitation with acids. Readily crystallizing salts areobtained by reacting the bases with oxalic acid.

Specific examples of herbicidal (hetaryloxy)- or aryloxyphenoxyaceticacid derivatives of the formula X whose toleration by crops can beimproved by substituted 5-aminopyrazoles I or I' are shown in Table 1below.

                  TABLE 1                                                         ______________________________________                                         ##STR18##                    X                                               No.  R.sup.a           R.sup.b                                                                              R.sup.c                                                                            Reference                                  ______________________________________                                        1.01                                                                                ##STR19##        CH.sub.3                                                                             CH.sub.3                                                                           DE-A 22 23 894                             1.02                                                                                ##STR20##        n- C.sub.4 H.sub.9                                                                   CH.sub.3                                                                           BE-A 868 875                               1.03                                                                                ##STR21##        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                           BE-A 858 618                               1.04                                                                                ##STR22##        CH.sub.3                                                                             CH.sub.3                                                                           BE-A 868 875                               1.05                                                                                ##STR23##        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                           DE-A 30 04 770                             ______________________________________                                    

Specific examples of herbicidal cyclohexenones of the formula XI whosetoleration by crops can be improved by substituted 5-aminopyrazoles I orI' are shown in Tables 2 to 13 below.

                                      TABLE 2                                     __________________________________________________________________________     ##STR24##                                                                                        Radicals on                                               No.                                                                              R.sup.d                                                                           R.sup.f      phenyl ring                                                                         phys. data/.sup.1 H-NMR [δ in ppm], mp.                                 [°C.]                                        __________________________________________________________________________    2.01                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       --    42-45                                               2.02                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       --    3.90(m, 2H), 4.20(t, 2H), 4.40(m, 2H),                                        6.80-7.00(m, 3H), 7.13-7.37(m, 2H)                  2.03                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       --    106-107                                             2.04                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       --    72-73                                               2.05                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   --    52-55                                               2.06                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   --    92                                                  2.07                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       2-F   76-78                                               2.08                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       2-F   72-77                                               2.09                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       2-F   121-125                                             2.10                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       2-F   103-107                                             2.11                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   2-F   82-86                                               2.12                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   2-F   81-85                                               2.13                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       3-F   62-68                                               2.14                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       3-F   3.90(m, 2H), 4.20(t, 2H), 4.40(m, 2H)                                         6.70(m, 3H), 7.25(m, 1H),                           2.15                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       3-F   103-109                                             2.16                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       3-F   73-79                                               2.17                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   3-F   4.20(t, 2H), 4.40(m, 2H)                                                      6.70(m, 3H), 7.25(m, 1H)                            2.18                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   3-F                                                       2.19                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       4-F   64-67                                               2.20                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       4-F   70-72                                               2.21                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       4-F   101-103                                             2.22                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       4-F   107-109                                             2.23                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   4-F   105-108                                             2.24                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   4-F   82-84                                               2.25                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       2-Cl  74-80                                               2.26                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       2-Cl  67-71                                               2.27                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       2-Cl  4.00(m, 2H), 4.27(t, 2H), 4.47(m, 2H),                                        7.20(t, 1H), 7.37(d, 1H)                            2.28                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       2-Cl  68-72                                               2.29                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   2-Cl  74-78                                               2.30                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   2-Cl  72-78                                               2.31                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       3-Cl                                                      2.32                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       3-Cl                                                      2.33                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       3-Cl                                                      2.34                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       3-Cl                                                      2.35                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   3-Cl                                                      2.36                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   3-Cl                                                      2.37                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       4-Cl  3.93(m, 2H), 4.20(t, 2H), 4.43(m, 2H),                                        6.90(m, 2H), 7.25(m, 2H)                            2.38                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       4-Cl  3.93(m, 2H), 4.20(t, 2H), 4.43(m, 2H),                                        6.90(m, 2H), 7.25(m, 2H)                            2.39                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       4-Cl  116-118                                             2.40                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       4-Cl  104-106                                             2.41                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   4-Cl  74-77                                               2.42                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   4-Cl  86-88                                               2.43                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       2-CF.sub.3                                                2.44                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       2-CF.sub.3                                                2.45                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       2-CF.sub.3                                                2.46                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       2-CF.sub.3                                                2.47                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   2-CF.sub.3                                                2.48                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   2-CF.sub.3                                                2.49                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       3-CF.sub.3                                                2.50                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       3-CF.sub.3                                                2.51                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       3-CF.sub.3                                                2.52                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       3-CF.sub.3                                                2.53                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   3-CF.sub.3                                                2.54                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   3-CF.sub.3                                                2.55                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       4-CF.sub.3                                                                          72-77                                               2.56                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       4-CF.sub.3                                                                          3.90(m, 2H), 4.27(t, 2H), 4.47(m, 2H)                                         7.00(d, 2H), 7.55(d, 2H)                            2.57                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       4-CF.sub.3                                                2.58                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       4-CF.sub.3                                                                          90-94                                               2.59                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   4-CF.sub.3                                                                          73-79                                               2.60                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   4-CF.sub.3                                                                          4.27(t, 2H), 4.47(m, 2H), 7.00(d, 2H)                                         7.55(d, 2H)                                         2.61                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       2,4-Cl.sub.2                                                                        73-75                                               2.62                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       2,4-Cl.sub.2                                                                        69-73                                               2.63                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       2,4-Cl.sub.2                                                                        4.00(m, 2H), 4.25(t, 2H), 4.45(t, 2H)                                         6.87(d, 1H), 7.17(d, 1H), 7.37(d, 1H)               2.64                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       2,4-Cl.sub.2                                                                        4.00(m, 2H), 4.25(t, 2H), 4.45(t, 2H)                                         6.87(d, 1H), 7.17(d, 1H), 7.37(d, 1H)               2.65                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   2,4-Cl.sub.2                                                                        4.25(t, 2H), 4.45(t, 2H), 6.87(d, 1H)                                         7.17(d, 1H), 7.37(d, 1H)                            2.66                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   2,4-Cl.sub.2                                                                        4.25(t, 2H), 4.45(t, 2H), 6.87(d, 1H)                                         7.17(d, 1H), 7.37(d, 1H)                            2.67                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       2,4,6-Cl.sub.3                                                                      90-93                                               2.68                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       2,4,6-Cl.sub.3                                                                      83-87                                               2.69                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       2,4,6-Cl.sub.3                                                                      79-82                                               2.70                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       2,4,6-Cl.sub.3                                                                      4.00(m, 2H), 4.27(t, 2H), 4.45(m, 2H),                                        7.32(s, 2H)                                         2.71                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   2,4,6-Cl.sub.3                                                                      105-108                                             2.72                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   2,4,6-Cl.sub.3                                                                      4.27(t, 2H), 4.45(m, 2H), 7.82(s, 2H)               2.73                                                                             Ethyl                                                                             Tetrahydropyran-3-yl                                                                       4-NO.sub.2                                                                          3.90(m, 2H), 4.32(m, 2H), 4.50(m, 2H),                                        7.00(d, 2H), 8.20(d, 2H)                            2.74                                                                             Propyl                                                                            Tetrahydropyran-3-yl                                                                       4-NO.sub.2                                                                          3.90(m, 2H), 4.32(m, 2H), 4.50(m, 2H)                                         7.00(d, 2H), 8.20(d, 2H)                            2.75                                                                             Ethyl                                                                             Tetrahydropyran-4-yl                                                                       4-NO.sub.2                                                                          126-129                                             2.76                                                                             Propyl                                                                            Tetrahydropyran-4-yl                                                                       4-NO.sub.2                                                                          138-141                                             2.77                                                                             Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   4-NO.sub.2                                                                          4.32(m, 2H), 4.50(m, 2H), 7.00(d, 2H),                                        8.20(d, 2H)                                         2.78                                                                             Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   4-NO.sub.2                                                                          4.32(m, 2H), 4.50(m, 2H), 7.00(d, 2H)                                         8.20(d, 2H)                                         __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR25##                                                                                           Radicals on                                            No. R.sup.d                                                                            R.sup.f       phenyl ring                                                                          phys. data/.sup.1 H-NMR [δ in ppm],                                     mp. [°C.]                                __________________________________________________________________________    3.01                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        --                                                     3.02                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        --                                                     3.03                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        --                                                     3.04                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        --                                                     3.05                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    --                                                     3.06                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    --                                                     3.07                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-F                                                    3.08                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-F                                                    3.09                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-F                                                    3.10                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-F                                                    3.11                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-F                                                    3.12                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-F                                                    3.13                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-Cl                                                   3.14                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-Cl                                                   3.15                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4 Cl   1.35(m, 3H), 4.05-4.30(m, 2H),                                                4.60(m, 1H), 6.80-7.40(m, 4H)                   3.16                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-Cl   1.35(m, 3H), 4.05-4.30(m, 2H),                                                4.60(m, 1H), 6.80-7.40(m, 4H)                   3.17                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-Cl   1.35(m, 3H), 4.05-4.25(m, 2H),                                                4.60(m, 1H), 6.80-7.40(m, 4H)                   3.18                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-Cl   1.35(m, 3H), 4.05-4.30(m, 2H),                                                4.60(m, 1H), 6.80-7.40(m,                       __________________________________________________________________________                                  4H)                                         

                                      TABLE 4                                     __________________________________________________________________________     ##STR26##                                                                                         Radicals on                                              No. R.sup.d                                                                           R.sup.f      phenyl ring                                                                         phys. data/.sup.1 H-NMR [δ in ppm], mp.                                 [°C.]                                       __________________________________________________________________________    4.01                                                                              Ethyl                                                                             Tetrahydropyran-3-yl                                                                       --    3.90(m, 2H), 4.23(t, 2H), 7.17-7.43(m, 5H)         4.02                                                                              Propyl                                                                            Tetrahydropyran-3-yl                                                                       --    65                                                 4.03                                                                              Ethyl                                                                             Tetrahydropyran-4-yl                                                                       --    3.97(m, 2H), 4.23(t, 2H), 7.17-7.43(m, 5H)         4.04                                                                              Propyl                                                                            Tetrahydropyran-4-yl                                                                       --    3.97(m, 2H), 4.23(t, 2H), 7.17-7.43(m, 5H)         4.05                                                                              Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   --    4.23(t, 2H), 7.17-7.43(m, 5H)                      4.06                                                                              Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   --    4.23(t, 2H), 7.17-7.43(m, 5H)                      4.07                                                                              Ethyl                                                                             Tetrahydropyran-3-yl                                                                       4-F   3.90(m, 2H), 4.17(t, 2H), 7.00(m, 2H),                                        7.40(m, 2H)                                        4.08                                                                              Propyl                                                                            Tetrahydropyran-3-yl                                                                       4-F   3.90(m, 2H), 4.17(t, 2H), 7.00(m, 2H),                                        7.40(m, 2H)                                        4.09                                                                              Ethyl                                                                             Tetrahydropyran-4-yl                                                                       4-F   4.00(m, 2H), 4.17(t, 2H), 7.00(m, 2H),                                        7.40(m, 2H)                                        4.10                                                                              Propyl                                                                            Tetrahydropyran-4-yl                                                                       4-F   4.00(m, 2H), 4.17(t, 2H), 7.00(m, 2H),                                        7.40(m, 2H)                                        4.11                                                                              Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   4-F   4.17(t, 2H), 7.00(m, 2H), 7.40(m, 2H),             4.12                                                                              Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   4-F   4.17(t, 2H), 7.00(m, 2H), 7.40(m, 2H),             4.13                                                                              Ethyl                                                                             Tetrahydropyran-3-yl                                                                       4-Cl  71-75                                              4.14                                                                              Propyl                                                                            Tetrahydropyran-3-yl                                                                       4-Cl  63-65                                              4.15                                                                              Ethyl                                                                             Tetrahydropyran-4-yl                                                                       4-Cl  4.00(m, 2H), 4.20(t, 2H), 7.30(m, 4H)              4.16                                                                              Propyl                                                                            Tetrahydropyran-4-yl                                                                       4-Cl  4.00(m, 2H), 4.20(t, 2H), 7.30(m, 4H)              4.17                                                                              Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   4-Cl  4.20(t, 2H), 7.30(m, 4H)                           4.18                                                                              Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   4-Cl  4.20(t, 2H), 7.30(m, 4H)                           4.19                                                                              Ethyl                                                                             Tetrahydropyran-3-yl                                                                       2-Cl  3.90(m, 2H), 4.25(t, 2H),                                                     7.10-7.50(m, 4H)                                   4.20                                                                              Propyl                                                                            Tetrahydropyran-3-yl                                                                       2-Cl  3.90(m, 2H), 4.25(t, 2H),                                                     7.10-7.50(m, 4H)                                   4.21                                                                              Ethyl                                                                             Tetrahydropyran-4-yl                                                                       2-Cl  4.00(m, 2H), 4.25(t, 2H),                                                     7.10-7.50(m, 4H)                                   4.22                                                                              Propyl                                                                            Tetrahydropyran-4-yl                                                                       2-Cl  4.00(m, 2H), 4.25(t, 2H),                                                     7.10-7.50(m, 4H)                                   4.23                                                                              Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   2-Cl  4.25(t, 2H) 7.10-7.50(m, 4H)                       4.24                                                                              Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   2-Cl  4.25(t, 2H) 7.10-7.50(m, 4H)                       4.25                                                                              Ethyl                                                                             Tetrahydropyran-3-yl                                                                       2,6-Cl.sub.2                                                                        3.90(m, 2H) 4.20(t, 2H), 7.20(t, 1H)                                          7.40(d, 2H)                                        4.26                                                                              Propyl                                                                            Tetrahydropyran-3-yl                                                                       2,6-Cl.sub.2                                                                        3.90(m, 2H) 4.20(t, 2H), 7.20(t, 1H)                                          7.40(d, 2H)                                        4.27                                                                              Ethyl                                                                             Tetrahydropyran-4-yl                                                                       2,6-Cl.sub.2                                                                        61-64                                              4.28                                                                              Propyl                                                                            Tetrahydropyran-4-yl                                                                       2,6-Cl.sub.2                                                                        4.00(m, 2H) 4.20(t, 2H), 7.20(t, 1H)                                          7.40(d, 2H)                                        4.29                                                                              Ethyl                                                                             Tetrahydrothiopyran-3-yl                                                                   2,6-Cl.sub.2                                                                        4.20(t, 2H) 7.20(t, 2H), 7.40(d, 2H)               4.30                                                                              Propyl                                                                            Tetrahydrothiopyran-3-yl                                                                   2,6-Cl.sub.2                                                                        4.20(t, 2H) 7.20(t, 2H), 7.40(d,                   __________________________________________________________________________                               2H)                                            

                                      TABLE 5                                     __________________________________________________________________________     ##STR27##                                                                                            Radicals on                                           No.  R.sup.d                                                                            R.sup.f       phenyl ring                                                                          phys. data/.sup.1 H-NMR [δ in ppm],                                     mp. [°C.]                               __________________________________________________________________________    5.01 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        --     3.90(m, 2H), 4.03(t, 2H), 4.23(t, 2H),                                        6.90(m, 3H), 7.27(m, 2H)                       5.02 Propyl                                                                             Tetrahydropyran-3-yl                                                                        --     3.90(m, 2H), 4.03(t, 2H), 4.23(t, 2H),                                        6.90(m, 3H), 7.27(m, 2H)                       5.03 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        --     3.97(m, 2H), 4.03(t, 2H), 4.23(t, 2H),                                        6.90(m, 3H), 7.27(m, 2H)                       5.04 Propyl                                                                             Tetrahydropyran-4-yl                                                                        --     3.97(m, 2H), 4.03(t, 2H), 4.23(t, 2H),                                        6.90(m, 3H), 7.27(m, 2H)                       5.05 Ethyl                                                                              Tetrahydrothiopyran-3-                                                                      --     4.03(t, 2H), 4.23(t, 2H), 6.90(m, 3H),                                        7.27(m, 2H)                                    5.06 Propyl                                                                             Tetrahydrothiopyran-3-                                                                      --     4.03(t, 2H), 4.23(t, 2H), 6.90(m, 3H),                                        7.27(m, 2H)                                    5.07 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        2-F    3.90(m, 2H), 4.10(t, 2H), 4.27(t, 2H),                                        6.80-7.15(m, 4H)                               5.08 Propyl                                                                             Tetrahydropyran-3-yl                                                                        2-F    3.90(m, 2H), 4.10(t, 2H), 4.27(t, 2H),                                        6.80-7.15(m, 4H)                               5.09 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        2-F    4.00(m, 2H), 4.10(t, 2H), 4.27(t, 2H),                                        6.80-7.15(m, 4H)                               5.10 Propyl                                                                             Tetrahydropyran-4-yl                                                                        2-F    76-80                                          5.11 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2-F    4.10(t, 2H), 4.27(t, 2H), 6.80-7.15(m,                                        4H),                                           5.12 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    2-F    4.10(t, 2H), 4.27(t, 2H), 6.80-7.15(m,                                        4H),                                           5.13 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        3-F    3.90(m, 2H), 4.05(t, 2H), 4.27(t, 2H),                                        6.67(m, 3H), 7.23(m, 1H)                       5.14 Propyl                                                                             Tetrahydropyran-3-yl                                                                        3-F    3.90(m, 2H), 4.05(t, 2H), 4.27(t, 2H),                                        6.67(m, 3H), 7.23(m, 1H)                       5.15 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        3-F    3.90-4.10(m, 4H), 4.27(t, 2H),                                                6.67(m, 3H), 7.23(m, 1H)                       5.16 Propyl                                                                             Tetrahydropyran-4-yl                                                                        3-F    3.90-4.10(m, 4H), 4.27(t, 2H),                                                6.67(m, 3H), 7.23(m, 1H)                       5.17 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    3-F    4.05(t, 2H), 4.27(t, 2H), 6.67(m, 3H)                                         7.23(m, 1H)                                    5.18 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    3-F    4.05(t, 2H), 4.27(t, 2H), 6.67(m, 3H)                                         7.23(m, 1H)                                    5.19 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-F    3.90(m, 2H), 4.03(t, 2H), 4.27(t, 2H),                                        6.90(m, 2H), 7.00(m, 2H)                       5.20 Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-F    3.90(m, 2H), 4.03(t, 2H), 4.27(t, 2H),                                        6.90(m, 2H), 7.00(m, 2H)                       5.21 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-F    3.90-4.06(m, 4H), 4.23(t, 2H),                                                6.90(m, 2H), 7.00(m, 2H)                       5.22 Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-F    3.90-4.06(m, 4H), 4.28(t, 2H),                                                6.90(m, 2H), 7.00(m, 2H)                       5.23 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-F    4.03(t, 2H), 4.27(t, 2H), 6.90(m, 2H),                                        7.00(m, 2H)                                    5.24 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-F    4.03(t, 2H), 4.27(t, 2H), 6.90(m, 2H),                                        7.00(m, 2H)                                    5.25 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        2-Cl                                                  5.26 Propyl                                                                             Tetrahydropyran-3-yl                                                                        2-Cl                                                  5.27 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        2-Cl                                                  5.28 Propyl                                                                             Tetrahydropyran-4-yl                                                                        2-Cl                                                  5.29 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2-Cl                                                  5.30 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    2-Cl                                                  5.31 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        3-Cl   3.90(m, 2H), 4.06(t, 2H), 4.27(t, 2H),                                        6.77(m, 1H), 6.90(m, 2H), 7.17(m, 1H)          5.32 Propyl                                                                             Tetrahydropyran-3-yl                                                                        3-Cl   3.90(m, 2H), 4.06(t, 2H), 4.27(t, 2H),                                        6.77(m, 1H), 6.90(m, 2H), 7.17(m, 1H)          5.33 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        3-Cl   3.90-4.10(m, 4H), 4.27(t, 2H),                                                6.77(m, 1H), 6.90(m, 2H), 7.17(m, 1H)          5.34 Propyl                                                                             Tetrahydropyran-4-yl                                                                        3-Cl   3.90-4.10(m, 4H), 4.27(t, 2H),                                                6.77(m, 1H), 6.90(m, 2H), 7.17(m, 1H)          5.35 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    3-Cl   4.06(t, 2H), 4.27(t, 2H), 6.77(m, 1H),                                        6.90(m, 2H), 7.17(m, 1H)                       5.36 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    3-Cl   4.06(t, 2H), 4.27(t, 2H), 6.77(m, 1H),                                        6.90(m, 2H), 7.17(m, 1H)                       5.37 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-Cl   3.90(m, 2H), 4.03(t, 2H), 4.23(t, 2H),                                        6.80(m, 2H), 7.20(m, 2H)                       5.38 Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-Cl   3.90(m, 2H), 4.03(t, 2H), 4.23(t, 2H),                                        6.80(m, 2H), 7.20(m, 2H)                       5.39 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-Cl   3.90-4.09(m, 4H), 4.23(t, 2H),                                                6.80(m, 2H), 7.20(m, 2H)                       5.40 Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-Cl   3.90-4.09(m, 4H), 4.23(t, 2H),                                                6.80(m, 2H), 7.20(m, 2H)                       5.41 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-Cl   4.03(t, 2H), 4.23(t, 2H), 6.80(m, 2H),                                        7.20(m, 2H)                                    5.42 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-Cl   4.03(t, 2H), 4.23(t, 2H), 6.80(m, 2H),                                        7.20(m, 2H)                                    5.43 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-NO.sub.2                                                                           3.90(m, 2H), 4.20(t, 2H), 4.28(t, 2H),                                        6.93(d, 2H), 8.20(d, H)                        5.44 Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-NO.sub.2                                                                           3.90(m, 2H), 4.20(t, 2H), 4.28(t, 2H),                                        6.93(d, 2H), 8.20(d, 2H)                       5.45 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-NO.sub.2                                                                           4.00(m, 2H), 4.20(t, 2H), 4.28(t, 2H),                                        6.93(d, 2H), 8.20(d, 2H)                       5.46 Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-NO.sub.2                                                                           4.00(m, 2H), 4.20(t, 2H), 4.28(t, 2H),                                        6.93(d, 2H), 8.20(d, 2H)                       5.47 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-NO.sub.2                                                                           4.20(t, 2H), 4.28(t, 2H), 6.93(d, 2H),                                        8.20(d, 2H)                                    5.48 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-NO.sub.2                                                                           4.20(t, 2H), 4.28(t, 2H), 6.93(d, 2H),                                        8.20(d, 2H)                                    5.49 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-Br   3.90(m, 2H), 4.00(t, 2H), 4.27(t, 2H),                                        6.80(d, 2H), 7.37(d, 2H)                       5.50 Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-Br   3.90(m, 2H), 4.00(t, 2H), 4.27(t, 2H),                                        6.80(d, 2H), 7.37(d, 2H)                       5.51 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-Br   3.90-4.10(m, 4H), 4.27(t, 2H),                                                6.80(d, 2H), 7.37(d, 2H)                       5.52 Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-Br   3.90-4.10(m, 4H), 4.27(t, 2H),                                                6.80(d, 2H), 7.37(d, 2H)                       5.53 Ethyl                                                                              Tetrahydrothiopyran-4-yl                                                                    4-Br   4.00(t, 2H), 4.27(t, 2H), 6.80(d, 2H),                                        7.37(d, 2H)                                    5.54 Propyl                                                                             Tetrahydrothiopyran-4-yl                                                                    4-Br   4.00(t, 2H), 4.27(t, 2H), 6.80(d, 2H),                                        7.37(d, 2H)                                    __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________     ##STR28##                                                                                           Radicals on                                            No. R.sup.d                                                                            R.sup.f       phenyl ring                                                                          phys. data/.sup.1 H-NMR [δ in ppm],                                     mp. [°C.]                                __________________________________________________________________________    6.01                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        --     3.90(m, 2H), 4.17(t, 2H), 7.10-7.40(m, 5H)      6.02                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        --     3.90(m, 2H), 4.17(t, 2H), 7.10-7.40(m, 5H)      6.03                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        --     4.00(m, 2H), 4.17(t, 2H), 7.10-7.40(m, 5H)      6.04                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        --     4.00(m, 2H), 4.17(t, 2H), 7.10-7.40(m, 5H)      6.05                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    --     4.17(t, 2H), 7.10-7.40(m, 5H)                   6.06                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    --     4.17(t, 2H), 7.10-7.40(m, 5H)                   6.07                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-F    3.90(m, 2H), 4.17(t, 2H), 7.00(t, 2H),                                        7.33(m, 2H)                                     6.08                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-F    3.90(m, 2H), 4.17(t, 2H), 7.00(t, 2H),                                        7.33(m, 2H)                                     6.09                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-F    4.00(m, 2H), 4.17(t, 2H), 7.00(t, 2H),                                        7.33(m, 2H)                                     6.10                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-F    4.00(m, 2H), 4.17(t, 2H), 7.00(t, 2H),                                        7.33(m, 2H)                                     6.11                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-F    4.17(t, 2H), 7.00(t, 2H), 7.33(m, 2H)           6.12                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-F    4.17(t, 2H), 7.00(t, 2H), 7.33(m, 2H)           6.13                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-Cl   3.90(m, 2H), 4.17(t, 2H), 7.27(s, 4H)           6.14                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-Cl   3.90(m, 2H), 4.17(t, 2H), 7.27(s, 4H)           6.15                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-Cl   4.00(m, 2H), 4.17(t, 2H), 7.27(s, 4H)           6.16                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-Cl   4.00(m, 2H), 4.17(t, 2H), 7.27(s, 4H)           6.17                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-Cl   4.17(t, 2H), 7.27(s, 4H)                        6.18                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-Cl   4.17(t, 2H), 7.27(s, 4H)                        6.19                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        2-Cl   3.90(m, 2H), 4.20(t, 2H), 7.07-7.40(m, 4H)      6.20                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        2-Cl   3.90(m, 2H), 4.20(t, 2H), 7.07-7.40(m, 4H)      6.21                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        2-Cl   4.00(m, 2H), 4.20(t, 2H), 7.07-7.40(m, 4H)      6.22                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        2-Cl   4.00(m, 2H), 4.20(t, 2H), 7.07-7.40(m, 4H)      6.23                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2-Cl   4.20(t, 2H), 7.07-7.40(m, 4H)                   6.24                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    2-Cl   4.20(t, 2H), 7.07-7.40(m, 4H)                   6.25                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        3-Cl   3.90(m, 2H), 4.20(t, 2H), 7.17(m, 3H)                                         7.30(m, 1H)                                     6.26                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        3-Cl   3.90(m, 2H), 4.20(t, 2H), 7.17(m, 3H)                                         7.30(m, 1H)                                     6.27                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        3-Cl   4.00(m, 2H), 4.20(t, 2H), 7.17(m, 3H)                                         7.30(m, 1H)                                     6.28                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        3-Cl   4.00(m, 2H), 4.20(t, 2H), 7.17(m, 3H)                                         7.30(m, 1H)                                     6.29                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    3-Cl   4.20(t, 2H), 7.17(m, 3H), 7.30(m, 1H)           6.30                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    3-Cl   4.20(t, 2H), 7.17(m, 3H), 7.30(m, 1H)           6.31                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        2,5-Cl.sub.2                                                                         3.90(m, 2H), 4.20(t, 2H), 7.07(dd, 1H),                                       7.20(d, 1H) 7.30(d, 1H)                         6.32                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        2,5-Cl.sub.2                                                                         3.90(m, 2H), 4.20(t, 2H), 7.07(dd, 1H),                                       7.20(d, 1H) 7.30(d, 1H)                         6.33                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        2,5-Cl.sub.2                                                                         4.00(m, 2H), 4.20(t, 2H), 7.07(dd, 1H),                                       7.20(d, 1H) 7.30(d, 1H)                         6.34                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        2,5-Cl.sub.2                                                                         4.00(m, 2H), 4.20(t, 2H), 7.07(dd, 1H),                                       7.20(d, 1H) 7.30(d, 1H)                         6.35                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2,5-Cl.sub.2                                                                         4.20(t, 2H), 7.07(dd, 1H), 7.20(d, 1H)                                        7.30(d, 1H)                                     6.36                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    2,5-Cl.sub.2                                                                         4.20(t, 2H), 7.07(dd, 1H), 7.20(d, 1H)                                        7.30(d, 1H)                                     6.37                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        2,6-Cl.sub.2                                                                         3.90(m, 2H), 4.20(t, 2H), 7.20(t, 1H)                                         7.40(d, 2H)                                     6.38                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        2,6-Cl.sub.2                                                                         3.90(m, 2H), 4.20(t, 2H), 7.20(t, 1H)                                         7.40(d, 2H)                                     6.39                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        2,6-Cl.sub.2                                                                         4.00(m, 2H), 4.20(t, 2H), 7.20(t, 1H)                                         7.40(d, 2H)                                     6.40                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        2,6-Cl.sub.2                                                                         4.00(m, 2H), 4.20(t, 2H), 7.20(t, 1H)                                         7.40(d, 2H)                                     6.41                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2,6-Cl.sub.2                                                                         4.20(t, 2H), 7.20(t, 1H), 7.40(d, 2H)           6.42                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    2,6-Cl.sub.2                                                                         4.20(t, 2H), 7.20(t, 1H), 7.40(d,               __________________________________________________________________________                                  2H)                                         

                                      TABLE 7                                     __________________________________________________________________________     ##STR29##                                                                                            Radicals on                                           No.  R.sup.d                                                                            R.sup.f       phenyl ring                                                                           phys. data/.sup.1 H-NMR [δ in ppm],                                     mp. [°C.]                              __________________________________________________________________________    7.01 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        --      3.90(m, 2H), 4.25(t, 2H), 4.58(s, 2H),                                        7.38(s, 5H)                                   7.02 Propyl                                                                             Tetrahydropyran-3-yl                                                                        --      3.90(m, 2H), 4.25(t, 2H), 4.58(s, 2H),                                        7.38(s, 5H)                                   7.03 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        --      4.03(m, 2H), 4.33(m, 2H), 4.60(s, 2H),                                        7.40(s, 5H)                                   7.04 Propyl                                                                             Tetrahydropyran-4-yl                                                                        --      4.03(m, 2H), 4.33(m, 2H), 4.60(s, 2H),                                        7.40(s, 5H)                                   7.05 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    --      4.27(s, 2H), 4.57(s, 2H), 7.35(s, 5H)         7.06 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    --      4.27(m, 2H), 4.57(s, 2H), 7.35(s, 5H)         7.07 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        2-F     3.93(m, 2H), 4.27(m, 2H), 4.67(s, 2H),                                        6.93-7.50(m, 4H)                              7.08 Propyl                                                                             Tetrahydropyran-3-yl                                                                        2-F     3.93(m, 2H), 4.27(m, 2H), 4.67(s, 2H),                                        6.93-7.50(m, 4H)                              7.09 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        2-F     4.03(m, 2H), 4.27(m, 2H), 4.63(s, 2H),                                        6.97-7.50(m, 4H)                              7.10 Propyl                                                                             Tetrahydropyran-4-yl                                                                        2-F     4.03(m, 2H), 4.27(m, 2H), 4.63(s, 2H),                                        6.97-7.50(m, 4H)                              7.11 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2-F     4.27(m, 2H), 4.67(s, 2H),                                                     6.97-7.50(m, 4H)                              7.12 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    2-F     4.27(m, 2H), 4.67(s, 2H),                                                     6.97-7.50(m, 4H)                              7.13 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        3-F     3.93(m, 2H), 4.27(m, 2H), 4.57(s, 2H),                                        6.90-7.15(m, 3H), 7.23-7.40(m, 1H)            7.14 Propyl                                                                             Tetrahydropyran-3-yl                                                                        3-F     3.93(m, 2H), 4.27(m, 2H), 4.57(s, 2H),                                        6.90-7.15(m, 3H), 7.23-7.40(s, 1H)            7.15 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        3-F     4.03(m, 2H), 4.25(m, 2H), 4.60(s, 2H),                                        6.90-7.18(m, 3H), 7.26-7.40(m, 1H)            7.16 Propyl                                                                             Tetrahydropyran-4-yl                                                                        3-F     4.03(m, 2H), 4.25(m, 2H), 4.60(s, 2H),                                        6.90-7.18(m, 3H), 7.26-7.40(m, 1H)            7.17 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    3-F     4.27(m, 2H), 4.60(s, 2H),                                                     6.90-7.15(m, 3H), 7.23-7.40(m, 1H)            7.18 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    3-F     4.27(m, 2H), 4.60(s, 2H),                                                     6.90-7.15(m, 3H), 7.23-7.40(m, 1H)            7.19 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-F     3.93(m, 2H), 4.23(m, 2H), 4.53(s, 2H),                                        7.00(m, 2H), 7.30(m, 2H)                      7.20 Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-F     3.93(m, 2H), 4.23(m, 2H), 4.53(s, 2H),                                        7.00(m, 2H), 7.30(m, 2H)                      7.21 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-F     92                                            7.22 Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-F     4.00(m, 2H), 4.23(m, 2H), 4.53(s, 2H),                                        7.03(m, 2H), 7.30(m, 2H)                      7.23 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-F     4.27(m, 2H), 4.53(s, 2H), 7.03(m, 2H),                                        7.30(m, 2H)                                   7.24 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-F     4.27(m, 2H), 4.53(s, 2H), 7.03(m, 2H),                                        7.30(m, 2H)                                   7.25 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        2-Cl                                                  7.26 Propyl                                                                             Tetrahydropyran-3-yl                                                                        2-Cl                                                  7.27 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        2-Cl                                                  7.28 Propyl                                                                             Tetrahydropyran-4-yl                                                                        2-Cl                                                  7.29 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2-Cl                                                  7.30 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    2-Cl                                                  7.31 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        3-Cl                                                  7.32 Propyl                                                                             Tetrahydropyran-3-yl                                                                        3-Cl                                                  7.33 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        3-Cl                                                  7.34 Propyl                                                                             Tetrahydropyran-4-yl                                                                        3-Cl                                                  7.35 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    3-Cl                                                  7.36 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    3-Cl                                                  7.37 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-Cl    3.93(m, 2H), 4.27(m, 2H), 4.53(s, 2H),                                        7.28(m, 4H)                                   7.38 Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-Cl    3.93(m, 2H), 4.27(m, 2H), 4.53(s, 2H),                                        7.28(m, 4H)                                   7.39 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-Cl    67-72                                         7.40 Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-Cl    4.00(m, 2H), 4.23(m, 2H), 4.53(s, 2H),                                        7.28(m, 4H)                                   7.41 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-Cl    4.27(m, 2H), 4.53(s, 2H), 7.28(m, 4H)         7.42 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-Cl    4.27(m, 2H), 4.53(s, 2H), 7.28(m, 4H)         7.43 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        2-CH.sub.3                                                                            3.93(m, 2H), 4.23(m, 2H), 4.57(s, 2H),                                        7.09-7.33(m, 4H)                              7.44 Propyl                                                                             Tetrahydropyran-3-yl                                                                        2-CH.sub.3                                                                            3.93(m, 2H), 4.23(m, 2H), 4.57(s, 2H),                                        7.09-7.33(m, 4H)                              7.45 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        2-CH.sub.3                                                                            4.00(m, 2H), 4.23(m, 2H), 4.57(s, 2H),                                        7.09-7.33(m, 4H)                              7.46 Propyl                                                                             Tetrahydropyran-4-yl                                                                        2-CH.sub.3                                                                            4.00(m, 2H), 4.23(m, 2H), 4.57(s, 2H),                                        7.09-7.33(m, 4H)                              7.47 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2-CH.sub.3                                                                            4.23(m, 2H), 4.57(s, 2H),                                                     7.09-7.33(m, 4H)                              7.48 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    2-CH.sub.3                                                                            4.23(m, 2H), 4.57(s, 2H),                                                     7.09-7.33(m, 4H)                              7.49 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        3-CH.sub.3                                                                            3.93(m, 2H), 4.25(m, 2H), 4.57(s, 2H),                                        7.00-7.32(m, 4H)                              7.50 Propyl                                                                             Tetrahydropyran-3-yl                                                                        3-CH.sub.3                                                                            3.93(m, 2H), 4.25(m, 2H), 4.57(s, 2H),                                        7.00-7.32(m, 4H)                              7.51 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        3-CH.sub.3                                                                            4.00(m, 2H), 4.27(m, 2H), 4.57(s, 2H),                                        7.00-7.32(m, 4H)                              7.52 Propyl                                                                             Tetrahydropyran-4-yl                                                                        3-CH.sub.3                                                                            4.00(m, 2H), 4.27(m, 2H), 4.57(s, 2H),                                        7.00-7.32(m, 4H)                              7.53 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    3-CH.sub.3                                                                            4.27(m, 2H), 4.60(s, 2H),                                                     7.00-7.32(m, 4H)                              7.54 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    3-CH.sub.3                                                                            4.27(m, 2H), 4.60(s, 2H),                                                     7.00-7.32(m, 4H)                              7.55 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-CH.sub.3                                                                            3.93(m, 2H), 4.20(m, 2H), 4.53(s, 2H),                                        7.07-7.30(m, 4H)                              7.56 Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-CH.sub.3                                                                            3.93(m, 2H), 4.20(m, 2H), 4.53(s, 2H),                                        7.07-7.30(m, 4H)                              7.57 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-CH.sub.3                                                                            4.00(m, 2H), 4.23(m, 2H), 4.57(s, 2H),                                        7.03-7.27(m, 4H)                              7.58 Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-CH.sub.3                                                                            4.00(m, 2H), 4.23(m, 2H), 4.57(s, 2H),                                        7.03-7.27(m, 4H)                              7.59 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-CH.sub.3                                                                            4.23(m, 2H), 4.57(s, 2H),                                                     7.07-7.30(m, 4H)                              7.60 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-CH.sub.3                                                                            4.28(m, 2H), 4.57(s, 2H),                                                     7.07-7.30(m, 4H)                              7.61 Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-tert.-C.sub.4 H.sub.9                                                               3.93(m, 2H), 4.23(m, 2H), 4.53(s, 2H),                                        7.20-7.40(m, 4H)                              7.62 Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-tert.-C.sub.4 H.sub.9                                                               3.93(m, 2H), 4.23(m, 2H), 4.53(s, 2H),                                        7.20-7.40(m, 4H)                              7.63 Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-tert.-C.sub.4 H.sub.9                                                               4.00(m, 2H), 4.23(m, 2H), 4.53(s, 2H),                                        7.20-7.40(m, 4H)                              7.64 Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-tert.-C.sub.4 H.sub.9                                                               4.00(m, 2H), 4.23(m, 2H), 4.53(s, 2H),                                        7.20-7.40(m, 4H)                              7.65 Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-tert.-C.sub.4 H.sub.9                                                               4.23(m, 2H), 4.53(s, 2H),                                                     7.20-7.40(m, 4H)                              7.66 Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-tert.-C.sub.4 H.sub.9                                                               4.23(m, 2H), 4.53(s, 2H),                                                     7.20-7.40(m, 4H)                              __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________     ##STR30##                                                                                           Radicals on                                            No. R.sup.d                                                                            R.sup.f       phenyl ring                                                                          phys. data/.sup.1 H--NMR [δ in ppm],                                    mp. [°C.]                                __________________________________________________________________________    8.01                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        --     3.73(s, 2H), 3.90(m, 2H), 4.17(t, 2H),                                        7.28(s, 5H)                                     8.02                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        --     3.73(s, 2H), 3.90(m, 2H), 4.17(t, 2H),                                        7.28(s, 5H)                                     8.03                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        --     3.77(s, 2H), 4.00(m, 2H), 4.13(t, 2H),                                        7.28(s, 5H)                                     8.04                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        --     3.77(s, 2H), 4.00(m, 2H), 4.13(t, 2H),                                        7.28(s, 5H)                                     8.05                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    --     3.80(s, 2H), 4.13(t, 2H), 7.28(s, 5H)           8.06                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    --     3.80(s, 2H), 4.13(t, 2H), 7.28(s, 5H)           8.07                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-F    3.72(s, 2H), 3.90(m, 2H), 4.13(t, 2H),                                        7.00(m, 2H), 7.30(m, 2H)                        8.08                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-F    3.72(s, 2H), 3.90(m, 2H), 4.13(t, 2H),                                        7.00(m, 2H), 7.30(m, 2H)                        8.09                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-F    63-65                                           8.10                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-F    3.73(s, 2H), 4.00(m, 2H), 4.13(t, 2H),                                        7.00(m, 2H), 7.30(m, 2H)                        8.11                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-F    3.75(s, 2H), 4.13(t, 2H), 7.00(m, 2H),                                        7.30(m, 2H)                                     8.12                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-F    3.75(s, 2H), 4.13(t, 2H), 7.00(m, 2H),                                        7.30(m, 2H)                                     8.13                                                                              Ethyl                                                                              Tetrahydropyran-3-yl                                                                        4-Cl   3.77(s, 2H), 3.93(m, 2H), 4.13(t, 2H),                                        7.30(s, 4H)                                     8.14                                                                              Propyl                                                                             Tetrahydropyran-3-yl                                                                        4-Cl   3.77(s, 2H), 3.93(m, 2H), 4.13(t, 2H),                                        7.30(s, 4H)                                     8.15                                                                              Ethyl                                                                              Tetrahydropyran-4-yl                                                                        4-Cl   3.73(s, 2H), 4.00(m, 2H), 4.17(t, 2H),                                        7.30(s, 4H)                                     8.16                                                                              Propyl                                                                             Tetrahydropyran-4-yl                                                                        4-Cl   3.73(s, 2H), 4.00(m, 2H), 4.17(t, 2H),                                        7.30(s, 4H)                                     8.17                                                                              Ethyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-Cl   3.73(s, 2H), 4.13(m, 2H), 7.30(s, 4H)           8.18                                                                              Propyl                                                                             Tetrahydrothiopyran-3-yl                                                                    4-Cl   3.73(s, 2H), 4.13(m, 2H), 7.30(s,               __________________________________________________________________________                                  4H)                                         

                                      TABLE 9                                     __________________________________________________________________________     ##STR31##                                                                                             Radicals on                                          No.  R.sup.d                                                                             R.sup.f       phenyl ring                                                                           phys. data/.sup.1 H--NMR [δ in                                          ppm], mp. [°C.]                       __________________________________________________________________________    9.01 Ethyl Tetrahydropyran-3-yl                                                                        --      3.70-4.20(m, 6H), 6.90(m, 3H),                                                7.30(m, 2H)                                  9.02 Propyl                                                                              Tetrahydropyran-3-yl                                                                        --      3.70-4.20(m, 6H), 6.90(m, 3H),                                                7.30(m, 2H)                                  9.03 Ethyl Tetrahydropyran-4-yl                                                                        --      3.83-4.23(m, 6H), 6.90(m, 3H),                                                7.30(m, 2H)                                  9.04 Propyl                                                                              Tetrahydropyran-4-yl                                                                        --      3.83-4.23(m, 6H), 6.90(m, 3H),                                                7.30(m, 2H)                                  9.05 Ethyl Tetrahydrothiopyran-3-yl                                                                    --      4.00(bs, 2H), 4.13(bs, 2H), 6.90(m, 3H)                                       7.30(m, 2H)                                  9.06 Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                    --      4.00(bs, 2H), 4.13(bs, 2H), 6.90(m, 3H)                                       7.30(m, 2H)                                  9.07 Ethyl Tetrahydropyran-3-yl                                                                        2-F     3.93(m, 2H), 4.00-4.20(m, 4H),                                                6.80-7.15(m, 4H)                             9.08 Propyl                                                                              Tetrahydropyran-3-yl                                                                        2-F     3.93(m, 2H), 4.00-4.20(m, 4H),                                                6.08-7.15(m, 4H)                             9.09 Ethyl Tetrahydropyran-4-yl                                                                        2-F     68-72                                        9.10 Propyl                                                                              Tetrahydropyran-4-yl                                                                        2-F     3.90-4.20(m, 6H), 6.80-7.15(m, 4H)           9.11 Ethyl Tetrahydrothiopyran-3-yl                                                                    2-F     4.00-4.20(m, 4H), 6.80-7.15(m, 4H)           9.12 Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2-F     4.00-4.20(m, 4H), 6.80-7.15(m, 4H)           9.13 Ethyl Tetrahydropyran-3-yl                                                                        3-F                                                  9.14 Propyl                                                                              Tetrahydropyran-3-yl                                                                        3-F                                                  9.15 Ethyl Tetrahydropyran-4-yl                                                                        3-F                                                  9.16 Propyl                                                                              Tetrahydropyran-4-yl                                                                        3-F                                                  9.17 Ethyl Tetrahydrothiopyran-3-yl                                                                    3-F                                                  9.18 Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                    3-F                                                  9.19 Ethyl Tetrahydropyran-3-yl                                                                        4-F     3.80-4.20(m, 6H), 6.75-7.05(m, 4H)           9.20 Propyl                                                                              Tetrahydropyran-3-yl                                                                        4-F     3.80-4.20(m, 6H), 6.75-7.05(m, 4H)           9.21 Ethyl Tetrahydropyran-4-yl                                                                        4-F     3.90-4.20(m, 6H), 6.75-7.05(m, 4H)           9.22 Propyl                                                                              Tetrahydropyran-4-yl                                                                        4-F     3.90-4.20(s, 6H), 6.75-7.05(m, 4H)           9.23 Ethyl Tetrahydrothiopyran-3-yl                                                                    4-F     3.90-4.20(m, 4H), 6.75-7.05(m, 4H)           9.24 Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-F     3.90-4.20(m, 4H), 6.75-7.05(m, 4H)           9.25 Ethyl Tetrahydropyran-3-yl                                                                        4-Cl    3.80-4.20(m, 6H), 6.80(m, 2H),                                                7.20(m, 2H)                                  9.26 Propyl                                                                              Tetrahydropyran-3-yl                                                                        4-Cl    3.80-4.20(m, 6H), 6.80(m, 2H),                                                7.20(m, 2H)                                  9.27 Ethyl Tetrahydropyran-4-yl                                                                        4-Cl    3.90-4.20(m, 6H), 6.80(m, 2H),                                                7.20(m, 2H)                                  9.28 Propyl                                                                              Tetrahydropyran-4-yl                                                                        4-Cl    3.90-4.20(m, 6H), 6.80(m, 2H),                                                7.20(m, 2H)                                  9.29 Ethyl Tetrahydrothiopyran-3-yl                                                                    4-Cl    3.90-4.20(m, 4H), 6.80(m, 2H),                                                7.20(m, 2H)                                  9.30 Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                    4-Cl    3.90-4.20(m, 4H), 6.80(m, 2H),                                                7.20(m, 2H)                                  9.31 Ethyl Tetrahydropyran-3-yl                                                                        2,6-Cl.sub.2                                                                          3.93(m, 2H), 4.00-4.25(m, 4H),                                                7.00(t, 1H), 7.30(d, 2H)                     9.32 Propyl                                                                              Tetrahydropyran-3-yl                                                                        2,6-Cl.sub.2                                                                          3.93(m, 2H), 4.00-4.25(m, 4H),                                                7.00(t, 1H), 7.30(d, 2H)                     9.33 Ethyl Tetrahydropyran-4-yl                                                                        2,6-Cl.sub.2                                                                          3.90-4.25(m, 6H), 7.00(t, 1H),                                                7.30(d, 2H)                                  9.34 Propyl                                                                              Tetrahydropyran-4-yl                                                                        2,6-Cl.sub.2                                                                          3.90-4.25(m, 6H), 7.00(t, 1H),                                                7.30(d, 2H)                                  9.35 Ethyl Tetrahydrothiopyran-3-yl                                                                    2,6-Cl.sub.2                                                                          4.00-4.20(m, 4H), 7.00(t, 1H),                                                7.30(d, 2H)                                  9.36 Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                    2,6-Cl.sub.2                                                                          4.00-4.20(m, 4H), 7.00(t, 1H),                                                7.30(d, 2H)                                  __________________________________________________________________________

                                      TABLE 10                                    __________________________________________________________________________     ##STR32##                                                                                               Radicals on                                        No.  R.sup.d                                                                             R.sup.f         phenyl ring                                                                           phys. data/.sup.1 H--NMR [δ in                                          ppm], mp. [°C.]                     __________________________________________________________________________    10.01                                                                              Ethyl Tetrahydropyran-3-yl                                                                          --      3.90(m, 2H), 4.20(m, 2H), 7.25(m, 5H)      10.02                                                                              Propyl                                                                              Tetrahydropyran-3-yl                                                                          --      3.90(m, 2H), 4.20(m, 2H), 7.25(m, 5H)      10.03                                                                              Ethyl Tetrahydropyran-4-yl                                                                          --                                                 10.04                                                                              Propyl                                                                              Tetrahydropyran-4-yl                                                                          --                                                 10.05                                                                              Ethyl Tetrahydrothiopyran-3-yl                                                                      --      4.20(m, 2H), 7.25(m, 5H)                   10.06                                                                              Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                      --      4.20(m, 2H), 7.25(m, 5H)                   10.07                                                                              Ethyl Tetrahydropyran-3-yl                                                                          4-F     3.90(m, 2H), 4.17(m, 2H), 6.93(m,                                             2H),                                                                          7.13(m, 2H)                                10.08                                                                              Propyl                                                                              Tetrahydropyran-3-yl                                                                          4-F     3.90(m, 2H), 4.17(m, 2H), 6.93(m,                                             2H),                                                                          7.13(m, 2H)                                10.09                                                                              Ethyl Tetrahydropyran-4-yl                                                                          4-F                                                10.10                                                                              Propyl                                                                              Tetrahydropyran-4-yl                                                                          4-F                                                10.11                                                                              Ethyl Tetrahydrothiopyran-3-yl                                                                      4-F     4.17(m, 2H), 6.93(m, 2H), 7.13(m, 2H)      10.12                                                                              Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                      4-F     4.17(m, 2H), 6.93(m, 2H), 7.13(m, 2H)      10.13                                                                              Ethyl Tetrahydropyran-3-yl                                                                          4-Cl    3.90(m, 2H), 4.17(m, 2H), 7.13(m, 4H)      10.14                                                                              Propyl                                                                              Tetrahydropyran-3-yl                                                                          4-Cl    3.90(m, 2H), 4.17(m, 2H), 7.13(m, 4H)      10.15                                                                              Ethyl Tetrahydropyran-4-yl                                                                          4-Cl                                               10.16                                                                              Propyl                                                                              Tetrahydropyran-4-yl                                                                          4-Cl                                               10.17                                                                              Ethyl Tetrahydrothiopyran-3-yl                                                                      4-Cl    4.17(m, 2H), 7.13(m, 4H)                   10.18                                                                              Propyl                                                                              Tetrahydrothiopyran-3-yl                                                                      4-Cl    4.17(m, 2H), 7.13(m,                       __________________________________________________________________________                                       4H)                                    

                                      TABLE 11                                    __________________________________________________________________________     ##STR33##                                                                                                  Radicals on                                     No.   R.sup.d                                                                              R.sup.f          phenyl ring                                                                            phys. data/.sup.1 H--NMR [δ                                             in ppm], mp. [°C.]              __________________________________________________________________________    11.01 Ethyl  Tetrahydropyran-3-yl                                                                           --       3.80-4.17(m, 6H), 6.90(m, 3H),                                                7.27(m, 2H)                            11.02 Propyl Tetrahydropyran-3-yl                                                                           --       3.80-4.17(m, 6H), 6.90(m, 3H),                                                7.27(m, 2H)                            11.03 Ethyl  Tetrahydropyran-4-yl                                                                           --       3.90-4.17(m, 6H), 6.90(m, 3H),                                                7.27(m, 2H)                            11.04 Propyl Tetrahydropyran-4-yl                                                                           --       3.90-4.17(m, 6H), 6.90(m, 3H),                                                7.27(m, 2H)                            11.05 Ethyl  Tetrahydrothiopyran-3-yl                                                                       --       3.97(t, 2H), 4.07(t, 2H), 6.90(m,                                             3H),                                                                          7.27(m, 2H)                            11.06 Propyl Tetrahydrothiopyran-3-yl                                                                       --       3.97(t, 2H), 4.07(t, 2H), 6.90(m,                                             3H),                                                                          7.27(m, 2H)                            11.07 Ethyl  Tetrahydropyran-3-yl                                                                           4-F      3.90(m, 4H), 4.03(t, 2H),                                                     6.70-7.03(m, 4H)                       11.08 Propyl Tetrahydropyran-3-yl                                                                           4-F      3.90(m, 4H), 4.03(t, 2H),                                                     6.70-7.03(m, 4H)                       11.09 Ethyl  Tetrahydropyran-4-yl                                                                           4-F      3.83-4.13(m, 6H), 6.70-7.03(m,                                                4H)                                    11.10 Propyl Tetrahydropyran-4-yl                                                                           4 F      3.83-4.13(m, 6H), 6.70-7.03(m,                                                4H)                                    11.11 Ethyl  Tetrahydrothiopyran-3-yl                                                                       4-F      3.90(t, 2H), 4.03(t, 2H)                                                      6.70-7.03(m, 4H)                       11.12 Propyl Tetrahydrothiopyran 3-yl                                                                       4-F      3.90(t, 2H), 4.03(t, 2H)                                                      6.70-7.03(m, 4H)                       11.13 Ethyl  Tetrahydropyran-3-yl                                                                           4-Cl     3.80-4.10(m, 6H), 6.80(d, 2H),                                                7.20(d, 2H)                            11.14 Propyl Tetrahydropyran-3-yl                                                                           4-Cl     3.80-4.10(m, 6H), 6.80(m, 2H),                                                7.20(d, 2H)                            11.15 Ethyl  Tetrahydropyran-4-yl                                                                           4-Cl     3.87-4.10(m, 6H), 6.80(d, 2H),                                                7.20(d, 2H)                            11.16 Propyl Tetrahydropyran-4-yl                                                                           4-Cl     3.87-4.10(m, 6H), 6.80(d, 2H),                                                7.20(d, 2H)                            11.17 Ethyl  Tetrahydrothiopyran-3-yl                                                                       4-Cl     54-61                                  11.18 Propyl Tetrahydrothiopyran-3-yl                                                                       4-Cl     3.90(t, 2H), 4.07(t, 2H), 6.80(d,                                             2H)                                                                           7.20(d, 2H)                            __________________________________________________________________________

                                      TABLE 12                                    __________________________________________________________________________     ##STR34##                                                  XI                No.                                                                              R.sup.d                                                                           R.sup.e            R.sup.f         R.sup.g                                                                          R.sup.h                                                                              R.sup.i                                                                         Reference               __________________________________________________________________________    12.1                                                                             C.sub.3 H.sub.7                                                                   CH.sub.2 CHCH.sub.2                                                                              CH.sub.3        CH.sub.3                                                                         CO.sub.2 CH.sub.3                                                                    Na                                                                              DE-A 2 439 104          12.2                                                                             C.sub.3 H.sub.7                                                                   CH.sub.2 CH.sub.3  CH.sub.2 CH(CH.sub.3)SCH.sub.2 CH.sub.3                                                       H  H      H DE-A 2 822 304          12.3                                                                             C.sub.2 H.sub.5                                                                   CH.sub.2 CHCHCl    CH.sub.2 CH(CH.sub.3)SCH.sub.2 CH.sub.3                                                       H  H      H US-A 4 440 566          12.4                                                                             C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCl    CH.sub.2 CH(CH.sub.3)SCH.sub.2 CH.sub.3                                                       H  H      H US-A 4 440 566          12.5                                                                             C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR35##      H  H      H EP-A 71 707             12.6                                                                             C.sub. 2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                                   ##STR36##      H  H      H EP-A 71 707             12.7                                                                             CH.sub.3                                                                          CH.sub.2 CHCHCH.sub.3                                                                             ##STR37##      H  H      H EP-A 71 707             12.8                                                                             C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR38##      H  H      H EP-A 71-707             12.9                                                                             C.sub.2 H.sub.5                                                                   CH.sub.2 CHCHCl                                                                                   ##STR39##      H  H      H EP-A 142 741            12.10                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR40##      H  H      H EP-A 66 195             12.11                                                                            C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                                   ##STR41##      H  H      H DE-A 24 39 104          12.12                                                                            C.sub.2 H.sub.5                                                                   CH.sub.2 CHCHCH.sub.3                                                                             ##STR42##      H  H      H DE-A 38 08 072          12.13                                                                            C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                                   ##STR43##      H  H      H EP-A 880 301            12.14                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCl                                                                                   ##STR44##      H  H      H EP-A 88 299             12.15                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCH.sub.3                                                                             ##STR45##      H  H      H EP-A 88 299             12.16                                                                            C.sub.2 H.sub.5                                                                   CH.sub.2 CHCHCH.sub.3                                                                             ##STR46##      H  H      H EP-A 238 021            12.17                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCH.sub.3                                                                             ##STR47##      H  H      H EP-A 238 021            12.18                                                                            C.sub.2 H.sub.5                                                                   CH.sub.2 CHCHCl                                                                                   ##STR48##      H  H      H EP-A 137 174            12.19                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR49##      H  H      H EP-A 2 137 200          12.20                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR50##      H  H      H EP-A 230 235            12.21                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCl                                                                                   ##STR51##      H  H      H EP-A 230 235            12.22                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCl                                                                                   ##STR52##      H  H      H EP-A 46 860             12.23                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR53##      H  H      H JP-A 540 191 945        12.24                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR54##      H  H      H EP-A 46 860             12.25                                                                            CH.sub.3                                                                          CH.sub.2 CHCHCl                                                                                   ##STR55##      H  H      H EP-A 88 299             12.26                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR56##      H  H      K EP-A 137 174            12.27                                                                            C.sub.2 H.sub.5                                                                   CH.sub.2 CHCHCl                                                                                   ##STR57##      H  H      H EP-A 46 860             12.28                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCH.sub.3                                                                             ##STR58##      H  H      H EP-A 125 094            12.29                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCl                                                                                   ##STR59##      H  H      H EP-A 125 094            12.30                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR60##      H  H      H EP-A 88 299             12.31                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCH.sub.2                                                                               ##STR61##      H  H      H EP-A 228 598            12.32                                                                            C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                                   ##STR62##      H  H      H EP-A 228 598            12.33                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR63##      H  H      H EP-A 66 195             12.34                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCHCl                                                                                   ##STR64##      H  H      H EP-A 66195              12.35                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCH.sub.2                                                                               ##STR65##      H  H      H EP-A 125 094            12.36                                                                            C.sub.3 H.sub.7                                                                   C.sub.3 H.sub.7    CH(SCH.sub.2 CH.sub.3).sub.2                                                                  H  H      H EP-A 230 260            12.37                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR66##      H  H      H EP-A 115 808            12.38                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5                                                                                   ##STR67##      H  H      H EP-A 115 808            12.39                                                                            C.sub.3 H.sub.7                                                                   C.sub.2 H.sub.5    CH.sub.3        CH.sub.3                                                                         C(CH.sub.3) NOCH.sub.3                                                               H EP-A 172 551            12.40                                                                            C.sub.3 H.sub.7                                                                   CH.sub.2 CHCH.sub.2                                                                               ##STR68##      OH H      H Proceedings Brit.                                                             Crop-Protection                                                               Conference- weeds                                                             1985 vol. 1 pp.                                                               93-98                   12.41                                                                            C.sub.2 H.sub.5                                                                    ##STR69##                                                                                        ##STR70##      H  H      H EP-A 38 38 309          12.42                                                                            C.sub.2 H.sub.5                                                                    ##STR71##                                                                                        ##STR72##      H  H      H EP-A 38 38 309          12.43                                                                            C.sub.2 H.sub.5                                                                    ##STR73##                                                                                        ##STR74##      H  H      H EP-A 38 38 309          12.44                                                                            n-C.sub.3 H.sub.7                                                                  ##STR75##                                                                                        ##STR76##      H  H      H EP-A 38 38 309          12.45                                                                            C.sub.2 H.sub.5                                                                    ##STR77##                                                                                        ##STR78##      H  H      H EP-A 38 38 309          12.46                                                                            n-C.sub.3 H.sub.7                                                                  ##STR79##                                                                                        ##STR80##      H  H      H EP-A 177 913            12.47                                                                            C.sub.2 H.sub.5                                                                    ##STR81##                                                                                        ##STR82##      H  H      H EP-A 177 913            12.48                                                                            C.sub.2 H.sub.5                                                                    ##STR83##                                                                                        ##STR84##      H  H      H EP-A 177 913            12.49                                                                            n-C.sub.3 H.sub.7                                                                  ##STR85##                                                                                        ##STR86##      H  H      H EP-A 177 913            12.50                                                                            n-C.sub.3 H.sub.7                                                                  ##STR87##                                                                                        ##STR88##      H  H      H EP-A 177 913            12.51                                                                            CH.sub.3                                                                           ##STR89##                                                                                        ##STR90##      H  H      H EP-A 177 913            12.52                                                                            C.sub.2 H.sub.5                                                                    ##STR91##                                                                                        ##STR92##      H  H      H EP-A 177                __________________________________________________________________________                                                          913                 

                                      TABLE 13                                    __________________________________________________________________________     ##STR93##                            XI                                                      Radicals on                                                   No. R.sup.d                                                                            R.sup.f                                                                              phenyl ring                                                                          phys. data [NMR* (δ in ppm)]                     __________________________________________________________________________    13.01                                                                             C.sub.2 H.sub.5                                                                     ##STR94##                                                                           4-F    2.9 (broad, 2H); 4.1 (broad, 2H)                       13.02                                                                             n-C.sub.3 H.sub.7                                                                   ##STR95##                                                                           4-F    2.9 (t, 2H); 4.05 (broad, 2H)                          13.03                                                                             C.sub.2 H.sub.5                                                                     ##STR96##                                                                           4-F    2.9 (t, 2H); 4.05 (broad, 2H)                          13.04                                                                             n-C.sub.3 H.sub.7                                                                   ##STR97##                                                                           4-F    2.9 (t, 2H); 4.05 (broad, 2H)                          13.05                                                                             C.sub.2 H.sub.5                                                                     ##STR98##                                                                           4-F    4.05 (broad, 2H)                                       13.06                                                                             n-C.sub.3 H.sub.7                                                                   ##STR99##                                                                           4-F    4.05 (broad, 2H)                                       13.07                                                                             C.sub.2 H.sub.5                                                                     ##STR100##                                                                          4-Cl   2.9 (t, 2H); 4.05 (broad, 2H)                          13.08                                                                             n-C.sub.3 H.sub.7                                                                   ##STR101##                                                                          4-Cl   2.9 (t, 2H); 4.05 (broad, 2H)                          13.09                                                                             C.sub.2 H.sub.5                                                                     ##STR102##                                                                          4-Cl   2.9 (t, 2H); 4.05 (broad, 2H)                          13.10                                                                             n-C.sub.3 H.sub.7                                                                   ##STR103##                                                                          4-Cl   2.9 (broad, 2H); 4.05 (broad, 2H)                      13.11                                                                             C.sub.2 H.sub.5                                                                     ##STR104##                                                                          4-Cl   4.05 (broad, 2H)                                       13.12                                                                             n-C.sub.3 H.sub.7                                                                   ##STR105##                                                                          4-Cl   4.05 (broad, 2H)                                       __________________________________________________________________________     *) selected signals                                                      

Herbicidal active ingredients and antidote compounds can be appliedtogether or separately, after emergence, to the leaves and shoots of thecrops and of the undesirable grasses. The antidote is preferably appliedsimultaneously with the herbicidal active ingredient. Separateapplication, where the antidote is first applied to the field, followedby the herbicidal active ingredient, is also possible. The herbicidalactive ingredient and the antidote can be formulated together orseparately as a spray in suspendable, emulsifiable or soluble form.

Antidote effects are also achieved by treating the seeds of crop plantsor the seedlings with the antidote before sowing or before planting out.The herbicidal active ingredient is then applied alone in theconventional manner.

In the treatment of seeds, in general amounts of active ingredient offrom 0.1 to 10 g, preferably from 1 to 2 g, per kilogram of seed arerequired.

In the application of the antidote by seed swelling or in the treatmentof seedlings, solutions which contain the antagonistic active ingredientin a concentration of from 1 to 10,000 ppm, in particular from 100 to10,000 ppm, are preferably used.

For herbicidal (hetaryloxy)- or aryloxyphenoxyacetic acid derivatives X,different amounts of an antidote compound are required if the herbicideis used in different crops. The ratios can be varied within wide ranges.They are also dependent on the structure of (hetaryloxy)- oraryloxyphenoxyacetic acid derivatives and on the particular target crop.Suitable weight ratios of herbicidal active ingredient to antidotecompound are from 1:10 to 1:0.01, preferably from 1:4to 1:0.1.

Different amounts of an antidote compound are required for the samecyclohexenone derivative XI if the latter is used in different crops.The ratios in which a cyclohexenone derivative and a substituted5-aminopyrazole I or I' are used can be varied within wide limits. Theyare dependent on the structure of the cyclohexenone derivative and ofthe substituted 5-aminopyrazole I or I' and on the particular crop.Suitable weight ratios of herbicidal active ingredient to antidotecompound are from 1:10 to 1:0.01, preferably from 1:4 to 1:0.25.

The novel agents or, in the case of separate application, the herbicidalactive ingredients and the antidote are applied, for example, in theform of directly sprayable solutions, powders, suspensions, includingconcentrated aqueous, oily or other suspensions, or dispersions,emulsions, oil dispersions, pastes, dusting agents, broadcasting agentsor granules, by spraying, atomizing, dusting, broadcasting or pouring.The application forms depend entirely on the intended uses.

For the preparation of directly sprayable solutions, emulsions, pastesand oil dispersions, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, such as coal tar oils and oils ofvegetable or animal origin, aliphatic, cyclic or aromatic hydrocarbons,eg. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylatednaphthalenes or derivatives thereof, for example methanol, ethanol,propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol,cyclohexanone, chlorobenzene or isophorone, or strongly polar solvents,such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone andwater, are suitable.

Aqueous application forms can be prepared from emulsion concentrates,pastes, wettable powders or oil dispersions by adding water. For thepreparation of emulsions, pastes or oil dispersions, the herbicidalactive ingredient and/or the antidote, as such or in solution in an oilor solvent, can be homogenized in water by means of wetting agents,adherents, dispersants or emulsifiers. However, it is also possible toprepare concentrates which consist of the herbicidal active ingredientand/or the antidote and wetting agents, adherents, dispersants oremulsifiers or possibly solvents or oil and which are suitable fordilution with water.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, alkali metaland alkaline earth metal salts of dibutylnaphthalenesulfonic acid,lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkalineearth metal salts of fatty acids, salts of sulfated hexadecanols,heptadecanols and octadecanols, salts of sulfated fatty alcohol glycolethers, condensates of sulfonated naphthalene and naphthalenederivatives with formaldehyde, condensates of naphthalene or ofnaphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyleneoctylethene ethers, ethoxylated isooctylphenol- [sic], octylphenol andnonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycolethers, alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, ligninsulfite wasteliquors and methylcellulose.

Powders, broadcasting agents and dusting agents can be prepared bymixing or milling the herbicidal active ingredient and/or the antidotetogether with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules, canbe prepared by binding the active ingredients to solid carriers.Examples of solid carriers are mineral earths, such as silica gel,silicas, silica gels, silicates, talc, kaolin, attaclay, limestone,chalk, talc, bole, loess, clay, dolomite, kieselguhr, calcium sulfate,magnesium sulfate, magnesium oxide, milled plastics, fertilizers, eg.ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, andvegetable products, such as grain flours, bark meal, wood meal andnutshell meal, cellulosic powders and other solid carriers.

The formulations contain from 0.01 to 95, preferably from 0.5 to 90%, byweight of herbicidal active ingredient and antidote. The applicationrates of herbicidal active ingredient are from 0.2 to 5 kg of activesubstance (a.s.) per hectare.

In addition to the substituted 5-aminopyrazole I or I' as the antidoteand the herbicide from the group consisting of the (hetaryloxy)- oraryloxyphenoxyacetic acids X or of the cyclohexenones XI, the novelherbicides may contain further herbicidal or growth-regulating activeingredients having a different chemical structure, the antagonisticeffect being retained.

EXAMPLE 1 1-Phenyl-4-cyano-5-(n-propylcarbonylamino)-pyrazole ##STR106##

6.8 ml (66 mmol) of butyryl chloride were added to a solution of 5.52 g(30 mmol) of 1-phenyl-4-cyano-5-aminopyrazole [known from J. Org. Chem.21 (1956), 1240] in 70 ml of pyridine. The mixture was heated for 15hours at 50° C. and then poured into 500 ml of 5% strength by weightaqueous hydrochloric acid. The product was extracted from the aqueousphase with methylene chloride and then isolated in a conventionalmanner. Yield: 50%.

EXAMPLE 2 1-Phenyl-4-cyano-5-(phenylureido)-pyrazole ##STR107##

9.0 g (80 mmol) of potassium tert-butylate and 8.7 ml (80 mmol) ofphenyl isocyanate were added to a solution of 5.52 g (30 mmol) of1-phenyl-4-cyano-5-aminopyrazole in 100 ml of toluene. The mixture washeated for 15 hours at 80° C. and then cooled, the insolubleconstituents were separated off and the resulting solution was acidifiedwith acetic acid, the product crystallizing out. Yield: 96%.

EXAMPLE 3 1-Phenyl-4-cyano-5-(dicyclohexylaminosulfonylureido)pyrazole##STR108##

4.4 ml (50 mmol) of chlorosulfonyl isocyanate were added to a solutionof 9.2 g (50 mmol) of 1-phenyl-4-cyano-5-aminopyrazole in 100 ml ofmethylene chloride. Stirring was carried out for 30 minutes at about 20°C., after which a solution of 7.5 ml (60 mmol) of triethylamine and 10ml (50 mmol) of dicyclohexylamine in 50 ml of methylene chloride wasslowly added dropwise. After the end of the addition, stirring wascontinued for a further hour and hydrolysis was then carried out with200 ml of water. The organic phase was separated off and was worked upin a conventional manner to give the product. Yield: 87%.

EXAMPLE 4 4-Cyano-1-phenyl-5-(N-phthalimido)-pyrazole ##STR109##

A mixture of 9.2 g (0.05 mol) of 1-phenyl- 4-cyano-5-aminopyrazole, 14.8g (0.1 mol) of phthalic anhydride and 100 ml of glacial acetic acid wasrefluxed for 4 hours, cooled to 25° C. and then diluted with 200 ml ofwater. The pH was then brought to 10 with 300 ml of 25% strength byweight aqueous sodium hydroxide solution, and the solid product was thenseparated off. Yield: 62%.

EXAMPLE 5 4-Cyano-1-methyl-5-(p-chlorobenzoylthioureido)-pyrazole##STR110##

6.4 ml (50 mmol) of p-chlorobenzoyl chloride were added to a solution of4.2 g (55 mmol) of ammonium isothiocyanate in 100 ml of acetone at about20° C. Stirring was carried out for 30 minutes, after which a solutionof 6.1 g (50 mmol) of 5-amino-4-cyano-1-methylpyrazole in 100 ml ofacetone was slowly added dropwise at 50° C. This mixture was heated atthe boil for 4 hours, cooled to about 25° C. and then diluted with 1000ml of water. The product was extracted with ethyl acetate. Yield: 65%.

The physical data of the end points [sic] I are shown in Table 14 below,which also lists further compounds I which were prepared, or can beprepared, by the same methods.

Table 15 summarizes the known compounds of type I', which, in additionto the compounds I, are preferred antidotes.

                                      TABLE 14                                    __________________________________________________________________________     ##STR111##                            I                                      Exp.                              mp.                                         No. R.sup.1                                                                          R.sup.4         R.sup.5    [°C.]                                __________________________________________________________________________    14.001                                                                        14.002                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2CH.sub.3                                                                            H                                                      14.003                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2CH.sub.2CH.sub.3                                                                    H          82-83                                       14.004                                                                            C.sub.6 H.sub.5                                                                  CO(CH.sub.2).sub.6CH.sub.3                                                                    H                                                      14.005                                                                            C.sub.6 H.sub.5                                                                  CO(CH.sub.2).sub.14CH.sub.3                                                                   H          72-76                                       14.006                                                                            C.sub.6 H.sub.5                                                                  COC(CH.sub.3).sub.3                                                                           H          163-168                                     14.007                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2C(CH.sub.3).sub.3                                                                   H                                                      14.008                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2Cl    H                                                      14.009                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2CH.sub.2Cl                                                                          H          124-130                                     14.010                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2CH.sub.2CH.sub. 2Cl                                                                 H          102-106                                     14.011                                                                            C.sub.6 H.sub.5                                                                  COCCl.sub.3     H                                                      14.012                                                                            C.sub.6 H.sub.5                                                                  COCF.sub.3      H          129-132                                     14.013                                                                            C.sub.6 H.sub.5                                                                  COC.sub.6 H.sub.5                                                                             H                                                      14.014                                                                            C.sub.6 H.sub.5                                                                  CO(4-CH.sub.3C.sub.6 H.sub.4)                                                                 H                                                      14.015                                                                            C.sub.6 H.sub.5                                                                  CO(2-ClC.sub.6 H.sub.4)                                                                       H                                                      14.016                                                                            C.sub.6 H.sub.5                                                                  CO(4-ClC.sub.6 H.sub.4)                                                                       H                                                      14.017                                                                            C.sub.6 H.sub.5                                                                  CO(2,4-Cl.sub.2C.sub.6 H.sub.3)                                                               H                                                      14.018                                                                            C.sub.6 H.sub.5                                                                  CO(2-NO.sub.2C.sub.6 H.sub.4)                                                                 H                                                      14.019                                                                            C.sub.6 H.sub.5                                                                  CO(3-NO.sub.2C.sub.6 H.sub.4)                                                                 H                                                      14.020                                                                            C.sub.6 H.sub.5                                                                  CO(4-NO.sub.2C.sub.6 H.sub.4)                                                                 H          205-209                                     14.021                                                                            C.sub.6 H.sub.5                                                                  SO.sub.2CH.sub.3                                                                              H          132-136                                     14.022                                                                            C.sub.6 H.sub.5                                                                  SO.sub.2C.sub.6 H.sub.5                                                                       H          118-126                                     14.023                                                                            C.sub.6 H.sub.5                                                                  SO.sub.2(4-ClC.sub.6 H.sub.4)                                                                 H          190-193                                     14.024                                                                            C.sub.6 H.sub.5                                                                  CONHCH.sub.3    H                                                      14.025                                                                            C.sub.6 H.sub.5                                                                  CONH(CH.sub.2).sub.3CH.sub.3                                                                  H                                                      14.026                                                                            C.sub.6 H.sub.5                                                                  CONHC.sub.6 H.sub.5                                                                           H          156-157                                     14.027                                                                            C.sub.6 H.sub.5                                                                  CONH(3,4-Cl.sub.2C.sub.6 H.sub.3                                                              H                                                      14.028                                                                            C.sub.6 H.sub.5                                                                  CSNHC.sub.6 H.sub.5                                                                           H          110-111                                     14.029                                                                            C.sub.6 H.sub.5                                                                  CONHSO.sub.2NHC.sub.6 H.sub.11                                                                H          115 (decomp).                               14.030                                                                            C.sub.6 H.sub.5                                                                  CONHSO.sub.2N(C.sub.6 H.sub.11).sub.2                                                         H          115 (decomp).                               14.031                                                                            C.sub.6 H.sub.5                                                                  CONHSO.sub.2NHC.sub.6 H.sub.5                                                                 H          110 (decomp).                               14.032                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.3      COCH.sub.3 112-113                                     14.033                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2CH.sub.3                                                                            COCH.sub.2CH.sub.3                                                                       78-84                                       14.034                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2C(CH.sub.3).sub.3                                                                   COCH.sub.2C(CH.sub.3).sub.3                                                              89-92                                       14.035                                                                            C.sub.6 H.sub.5                                                                  CO(2,4-Cl.sub.2C.sub.6 H.sub.3)                                                               CO(2,4-Cl.sub.2C.sub.6 H.sub.3)                                                          146-148                                     14.036                                                                            C.sub.6 H.sub.5                                                                  CO(2-NO.sub.2C.sub.6 H.sub.4)                                                                 CO(2-NO.sub.2C.sub.6 H.sub.4)                                                            184-194                                     14.037                                                                                ##STR112##                183-190                                     14.038                                                                            C.sub.6 H.sub.5                                                                  SO.sub.2(4-CH.sub.3C.sub.6 H.sub.4)                                                           SO.sub.2(4-CH.sub.3C.sub.6 H.sub.4)                                                      155-156                                     14.039                                                                            C.sub.6 H.sub.5                                                                  SO.sub.2(4-ClC.sub.6 H.sub.4)                                                                 SO.sub.2(4-ClC.sub.6 H.sub.4)                                                            190-193                                     14.040                                                                            C.sub.6 H.sub.5                                                                  Co-Cyclopropyl  H          143-145                                     14.041                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2C.sub.6 H.sub.5                                                                     H          142-144                                     14.042                                                                            C.sub.6 H.sub.5                                                                  COCH.sub.2CH.sub.2C.sub.6 H.sub.5                                                             H          128-130                                     14.043                                                                            C.sub.6 H.sub.5                                                                  CHC.sub.6 H.sub.5          87-93                                       14.044                                                                            C.sub.6 H.sub.5                                                                  CH(4-ClC.sub.6 H.sub.4)    126-129                                     14.045                                                                            C.sub.6 H.sub.5                                                                  CH(2-ClC.sub.6 H.sub.4)    128-130                                     14.046                                                                            CH.sub.3                                                                         COCH.sub.2CH.sub.3                                                                            H                                                      14.047                                                                            CH.sub.3                                                                         COCH.sub.2CH.sub.2CH.sub.3                                                                    H          86-90                                       14.048                                                                            CH.sub.3                                                                         CO(CH.sub.2).sub.6CH.sub.3                                                                    H                                                      14.049                                                                            CH.sub.3                                                                         CO(CH.sub.2).sub.14CH.sub.3                                                                   H          92-94                                       14.050                                                                            CH.sub.3                                                                         COC(CH.sub.3).sub.3                                                                           H          129-131                                     14.051                                                                            CH.sub.3                                                                         COCH.sub.2C(CH.sub.3).sub.3                                                                   H          103-104                                     14.052                                                                            CH.sub.3                                                                         COCH.sub.2CH.sub.2Cl                                                                          H                                                      14.053                                                                            CH.sub.3                                                                         COCH.sub.2CH.sub.2CH.sub.2Cl                                                                  H          oil                                         14.054                                                                            CH.sub.3                                                                         COCCl.sub.3     H                                                      14.055                                                                            CH.sub.3                                                                         COCF.sub.3      H                                                      14.056                                                                            CH.sub.3                                                                         CO(4-CH.sub.3C.sub.6 H.sub.4)                                                                 H                                                      14.057                                                                            CH.sub.3                                                                         CO(2-ClC.sub.6 H.sub.4)                                                                       H                                                      14.058                                                                            CH.sub.3                                                                         CO(2,4-Cl.sub.2C.sub.6 H.sub.3)                                                               H          193-194                                     14.059                                                                            CH.sub.3                                                                         CO(2-NO.sub.2C.sub.6 H.sub.4)                                                                 H          222-226                                     14.060                                                                            CH.sub.3                                                                         CO(3-NO.sub.2C.sub.6 H.sub.4)                                                                 H                                                      14.061                                                                            CH.sub.3                                                                         CO(4-NO.sub.2C.sub.6 H.sub.4)                                                                 H          181-182                                     14.062                                                                            CH.sub.3                                                                         SO.sub.2CH.sub.3                                                                              H          120-123                                     14.063                                                                            CH.sub.3                                                                         SO.sub.2C.sub.6 H.sub.5                                                                       H          190-197                                     14.064                                                                            CH.sub.3                                                                         SO.sub.2(4-ClC.sub.6 H.sub.4)                                                                 H          209-210                                     14.065                                                                            CH.sub.3                                                                         CONHCH.sub.3    H                                                      14.066                                                                            CH.sub.3                                                                         CONH (CH.sub.2).sub.3CH.sub.3                                                                 H                                                      14.067                                                                            CH.sub.3                                                                         CONHC.sub.6 H.sub.5                                                                           H                                                      14.068                                                                            CH.sub.3                                                                         CONH(3,4-Cl.sub.2C.sub.6 H.sub.3)                                                             H                                                      14.069                                                                            CH.sub.3                                                                         CSNHC.sub.6 H.sub.5                                                                           H                                                      14.070                                                                            CH.sub.3                                                                         CONHSO.sub.2NHC.sub.6 H.sub.11                                                                H                                                      14.071                                                                            CH.sub.3                                                                         CONHSO.sub.2N(C.sub.6 H.sub.11).sub.2                                                         H          100 (decomp.)                               14.072                                                                            CH.sub.3                                                                         CSNHCOC.sub.6 H.sub.5                                                                         H          140                                         14.073                                                                            CH.sub.3                                                                         CSNHCO(2-ClC.sub.6 H.sub.4)                                                                   H          168                                         14.074                                                                            CH.sub.3                                                                         CSNHCO(4-ClC.sub.6 H.sub.4)                                                                   H          215-217                                     14.075                                                                            CH.sub.3                                                                         CSNHCO(2-NO.sub.2C.sub.6 H.sub.4)                                                             H          141 (decomp.)                               14.076                                                                            CH.sub.3                                                                         CSNHCO(3-NO.sub.2C.sub.6 H.sub.4)                                                             H          144-148                                     14.077                                                                            CH.sub.3                                                                         CSNHCO(4-NO.sub.2C.sub.6 H.sub.4)                                                             H          >240                                        14.078                                                                            CH.sub.3                                                                         COC(CH.sub.3).sub.3                                                                           COC(CH.sub.3).sub.3                                                                      111-113                                     14.079                                                                            CH.sub.3                                                                         SO.sub.2(4-CH.sub.3C.sub.6 H.sub.4)                                                           SO.sub.2(4-CH.sub.3C.sub.6 H.sub.4)                                                      176-180                                     14.080                                                                            CH.sub.3                                                                         SO.sub. 2C.sub.6 H.sub.5                                                                      SO.sub.2C.sub.6 H.sub.5                                                                  190-197                                     14.081                                                                            CH.sub.3                                                                         CO-Cyclopropyl  H          170-173                                     14.082                                                                            CH.sub.3                                                                         COCH.sub.2C.sub.6 H.sub.5                                                                     H          122-125                                     14.083                                                                            CH.sub.3                                                                         COCH.sub.2CH.sub.2C.sub.6 H.sub.5                                                             H          114-116                                     14.084                                                                            CH.sub.3                                                                         CHC.sub.6 H.sub.5          113-115                                     14.085                                                                            CH.sub.3                                                                         CH(4-ClC.sub.6 H.sub.4)    110-111                                     14.086                                                                            CH.sub.3                                                                         CH(2-ClC.sub.6 H.sub.4)    145-147                                     __________________________________________________________________________

                  TABLE 15                                                        ______________________________________                                        Known 5-aminopyrazoles I'                                                      ##STR113##                    I'                                             Exp.                               mp.                                        No.  R.sup.1     R.sup.2                                                                              R.sup.4    [°C.]                                                                         Ref.                                ______________________________________                                        15.01                                                                              CH.sub.3    H      H          222-223                                                                              1/3                                 15.02                                                                              C.sub.6 H.sub.5                                                                           H      H          158-160                                                                              1/3                                 15.03                                                                              4-ClC.sub.6 H.sub.5                                                                       H      H          167-167.5                                                                            1/3                                 15.04                                                                              4-NO.sub.2C.sub.6 H.sub.4                                                                 H      H          224-225                                                                              1                                   15.05                                                                              CH.sub.3    CH.sub.3                                                                             H          194    1                                   15.06                                                                              C.sub.6 H.sub.5                                                                           CH.sub.3                                                                             H          132-133                                                                              1                                   15.07                                                                              C.sub.6 H.sub.5                                                                           CF.sub.3                                                                             H          115-116                                                                              2                                   15.08                                                                              4-NO.sub.2C.sub.6 H.sub.5                                                                 CF.sub.3                                                                             H          213-214                                                                              2                                   15.09                                                                              H           CH.sub.3                                                                             H          163    1                                   15.10                                                                              2,4-Cl.sub.2C.sub.6 H.sub.3                                                               H      H          141-142                                                                              4                                   15.11                                                                              CH.sub.2 CH.sub.2 OH                                                                      H      H          158-160                                                                              1                                   15.12                                                                              4-Br-C.sub.6 H.sub.4                                                                      H      H          168-170                                                                              1                                   15.13                                                                              2-ClC.sub.6 H.sub.4                                                                       H      H          124    1                                   15.14                                                                              2-CH.sub.3C.sub.6 H.sub.4                                                                 H      H          158-159                                                                              1                                   15.15                                                                              C.sub.6 H.sub.5                                                                           H      COCH.sub.3 95-97                                      15.16                                                                              CH.sub.3    H      COCH.sub.3 120-130                                    15.17                                                                              CH.sub.3    H      COCH.sub.2 Cl                                         15.18                                                                              CH.sub.3    H      COC.sub.6 H.sub.5                                                                        173-174                                    15.19                                                                              CH.sub.3    H      CO-(4-Cl--C.sub.6 H.sub.4)                            15.20                                                                              CH.sub.3    H      CO-Cyclohexyl                                                                            154-156                                    ______________________________________                                    

References:

[1] K. Robins et al., J. Org. Chem. 21 (1956), 1240

[2] K. Tanaka et al., Bull. Chem. Soc. Jpn. 60 (1987), 4480

[3] R. J. Quinn et al., Aust. J. Chem. Soc. 42 (1989), 747

[4] P. L. Southwick et al., J. Heterocycl. Chem. 12 (1975), 1199

Examples of biological action

The effect of various novel herbicides or herbicide combinationsconsisting of the herbicide and the antidote compound on the growth ofdesired and undesirable plants in comparison with the herbicidal activeingredient alone is demonstrated by the following biological examplesfrom greenhouse experiments:

In the greenhouse experiments, the culture vessels used were plasticflower pots having a capacity of about 300 cm³ and containing loamy sandwith about 3.0% of humus as a substrate. The seeds of the test plantswere sown shallowly and separately according to species and weremoistened. Thereafter, the vessels were covered with transparent plasticcovers until the seeds had uniformly germinated and the plants had begunto grow.

List of test plants

    ______________________________________                                        Botanical name     Common name                                                ______________________________________                                        Brachiaria platphylla                                                                            Broadleaf signalgrass                                      Triticum aestivum  Spring wheat                                               Zea mays           Indian corn                                                ______________________________________                                    

For the postemergence treatment, the test plants are first growncultivated to a height of 3 to 20 cm, depending on the form of growth,before being treated. The herbicides were suspended or emulsified inwater as a distributing agent and sprayed by means of finelydistributing nozzles.

The herbicide used as an example of the cyclohexenone derivative of theformula XI was ##STR114##

For the postemergence treatment, all antidote compounds were prepared ina mixture consisting of 80% by weight of cyclohexenone as solvent and20% by weight of surfactant (Emulphor EL*.sup.)) with 10% by weight ofactive ingredient.

For comparison, the herbicidal active ingredient 12.42 was formulated asa 10-20% by weight emulsion concentrate and was used in the spray liquorin each case with the addition of the amount of solvent system withwhich the antidote compound were applied at the application rates shown[lacuna] Tables. The solution was prepared by mixing the activeingredient into a solution of 93% by weight of xylene and 7% by weightof Lutensol® AP-8**.sup.)).

After application of the active ingredient mixtures, the test plantswere cultivated in a greenhouse, warmth-loving species at about 18°-30°C. and those from more temperate climates at about 10°-25° C.

The test period extended over from 3 to 5 weeks. During this time, theplants were tended and their reaction to the individual treatments wasrecorded.

The damage caused by the chemical agents was evaluated on the basis of ascale from 0 to 100% in comparison with the untreated control plants. 0means no damage and 100 means complete destruction of the plants.

Table 16 documents the antagonistic action of the novel examplecompounds No. 14.028, 14.058, 14.059 and 15.18.

TABLE 16

Improvement of the toleration of the herbicide 12.42 by corn as a resultof admixing an antagonistic substituted 5-aminopyrazole duringpostemergence application:

    ______________________________________                                        Greenhouse experiment                                                               Application                                                             Anti- rate          Test plants and damage [%]                                dote  [kg/ha a.s.]  Crop      Undesirable plant                               No.   Herbicide Antidote                                                                          Zea mays.sup.1)                                                                         Brachiaria platphylla                           ______________________________________                                        --    0.06          40        90                                              5.18  0.06 + 0.06   10        80                                              4.058 0.06 + 0.06   20        100                                             4.059 0.06 + 0.06   15        80                                              4.028 0.06 + 0.06   20        75                                              ______________________________________                                         .sup.1) Lixis variety                                                    

Table 16 shows that the substituted 5-aminopyrazoles increase thetoleration of the herbicide 12.42 by crops from the Gramineae family(grasses).

We claim:
 1. A substituted 5-aminopyrazole of the formula I ##STR115##where R¹ is C₁ -C₈ -alkyl, C₁ -C₈ -hydroxyalkyl or a phenyl group whichmay carry from one to three of the following radicals: halogen, nitro,C₁ -C₄ -alkyl, partially or completely halogenated C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, partially or completely halogenated C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio or --NR⁶ R⁷, where R⁶ and R⁷ are each hydrogen or C₁ -C₄-alkyl, and the phenyl group may additionally carry a number of halogenatoms so that the total number of radicals is 4 or 5;R² is hydrogen orC₁ -C₄ -alkyl which may be unsubstituted or partially or completelyhalogenated; R³ is cyano or CO--R⁸ or CS--R⁸, where R⁸ is hydroxyl, C₁-C₄ -alkoxy, amino, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino; R⁴ andR⁵ are each hydrogen, C₁ -C₄ -alkyl, PX(OR⁹)₂, SO₂ --R⁹, CX--R¹⁰,CX--NH--CY--R⁹ or CX--NH--SO₂ --R¹¹, where X and Y are each oxygen orsulfur; R⁹ is one of the substituents R¹ ; R¹⁰ is C₁ -C₂₀ -alkyl, C₁ -C₄-alkoxy or a phenyl group which may carry from one to three of thefollowing radicals: halogen, nitro, C₁ -C₄ -alkyl, partially orcompletely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, partially orcompletely halogenated C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio or --NR⁶ R⁷,and which may additionally carry a further number of halogen atoms sothat the total number of radicals is 5; amino which may be unsubstitutedor may carry a C₁ -C₄ -alkyl, cycloalkyl or phenyl radical, where thephenyl radical may additionally carry from one to three of the followingradicals: halogen, C₁ -C₄ -alkyl, partially or completely halogenated C₁-C₄ -alkyl, C₁ -C₄ -alkoxy, partially or completely halogenated C₁ -C₄-alkoxy or C₁ -C₄ -alkylthio, and the phenyl group may additionallycontain a further number of halogen atoms so that the total number ofradicals is 4 or 5; R¹¹ is amino, C₁ -C₄ -alkylamino, di-C₁ -C₄-alkylamino, pyrrolidinyl, piperidinyl or morpholinyl;or R⁴ and R⁵together form a group ═CR¹² R¹³ or --CO--W--CO--, where R¹² is hydrogen,amino, C₁ -C₄ -alkylamino or C₃ --C₈ -cycloalkylamino; R¹³ is amino, C₁-C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₃ -C₈ -cycloalkylamino,pyrrolidin-1-yl, piperidin-1-yl, morpholin-4-yl, phenyl or pyridyl,where the two last-mentioned substituents may furthermore carry from oneto three of the following radicals: halogen, nitro, C₁ -C₄ -alkyl,partially or completely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,partially or completely halogenated C₁ -C₄ -alkoxy or C₁ -C₄ -alkylthio;W is an ethylene or ethenylene bridge, a 5-membered or 6-membered1,2-C-bonded aromatic or heteroaromatic bridge having a nitrogen, oxygenor sulfur atom as the hetero atom, where these bridge members mayfurthermore carry, on each substitutable carbon atom, a radical selectedfrom up to 2 of the following: halogen, C₁ -C₄ -alkyl, partially orcompletely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, partially orcompletely halogenated C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio and partiallyor completely halogenated C₁ -C₄ -alkylthio, and where the bridgemembers may additionally carry a number of halogen atoms equivalent tothe number of further substitutable carbon atoms, or a 5-membered or6-membered 1,2-C-bonded cycloalkylene or cycloalkenylene bridge, wherethese substituents may furthermore carry from one to four of thefollowing radicals: halogen or C₁ -C₄ -alkyl; and the basic salts of thecompounds I in which R³ is hydroxycarbonyl or hydroxythiocarbonyl, andthe acidic salts of the compounds I which contain a basic nitrogen atom,with the exception of 1-phenyl- and1-methyl-4-cyano-5-acylaminopyrazole,1-methyl-4-cyano-5-(chloromethylcarbonylamino)-pyrazole,1-methyl-4-cyano-5-(phenylcarbonylamino)-pyrazole,1-methyl-4-cyano-5-(p-chlorophenylcarbonylamino)-pyrazole,5-amino-4-cyano-1-methylpyrazole, 5-amino-4-cyano-1,3-dimethylpyrazole,5-amino-4-cyano-1-methyl-3-trifluoromethylpyrazole,5-amino-1,3-dimethylpyrazole-4-carboxamide,5-amino-1-methylpyrazole-4-carboxamide,5-amino-1-(2-hydroxyethyl)-pyrazole-4-carboxamide,5-amino-4-cyano-1-(2-hydroxyethyl)-pyrazole and those compounds I inwhich either R¹ is unsubstituted or substituted phenyl and R⁴ and R⁵ aresimultaneously hydrogen or R¹ is unsubstituted or substituted phenyl, R²and R⁵ are each hydrogen, R³ is cyano and R⁴ is hydrogen or C₁ -C₄-alkylamino or R¹ is substituted phenyl, R² and R⁵ are each hydrogen, R³is cyano, C₁ -C₄ -alkoxycarbonyl, aminocarbonyl or C₁ -C₄-alkylaminocarbonyl and R⁴ is CX--(C₁ -C₄ -alkoxy), or substituted orunsubstituted CX--NH₂, and with the exception of those compounds I inwhich one of the radicals R⁴ or R⁵ is C₁ -C₃ -alkyl and the other ismethoxycarbonyl or ethoxycarbonyl when R² is hydrogen, R³ is cyano andR¹ is substituted phenyl.
 2. A substituted 5-aminopyrazole I as definedin claim 1, wherein R³ is cyano.
 3. A herbicidal composition containingone or more substituted 5-aminopyrazoles of the formula I', where I'corresponds to the definition of I without the exception, and one ormore herbicidal active ingredients from the group consisting ofA) the2-(4-hetaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivatives of theformula X ##STR116## where R^(a) is phenyl, pyridyl, benzoxazyl,benzothiazyl or benzopyrazinyl, where these aromatic ring systems maycarry up to two of the following radicals: halogen, nitro, C₁ -C₄-alkyl, partially or completely halogenated C₁ -C₄ -alkyl or partiallyor completely halogenated C₁ -C₄ -alkoxy; R^(b) is hydrogen, C₁ -C₅-alkyl, C₃ -C₅ -alkylideneimino, C₃ -C₅ -alkylideneiminoxy-C₂ - or -C₃-alkyl or one equivalent of a plant-tolerated cation and R^(c) ishydrogen or methyl,or B) the cyclohexenone derivatives of the formula XI##STR117## where R^(d) is C₁ -C₄ -alkyl; R^(e) is C₁ -C₄ -alkyl, C₃ - orC₄ -alkenyl, C₃ - or C₄ -alkynyl or partially or completely halogenatedC₃ - or C₄ -alkenyl; a C₁ -C₄ -alkylene or C₂ -C₄ -alkenyl chain, bothof which may furthermore carry from 1 to 3 C₁ -C₃ -alkyl radicals and/orhalogen atoms, or a 3-membered to 6-membered alkylene or 4-membered to6-membered alkenylene chain which, if desired, is substituted by C₁ -C₃-alkyl and each of which contains, as a chain member, an oxygen orsulfur atom which is not directly adjacent to the oxime ether moiety,all abovementioned chains carrying a terminal phenyl ring which in turnmay be substituted by from one to three radicals selected from the groupconsisting of a benzyloxycarbonyl or phenyl radical and from one tothree of each of the following radicals: nitro, cyano, halogen, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C¹ -C₄ -alkylthio, partially or completelyhydrogenated C₁ -C₄ -alkyl, partially or completely halogenated C¹ -C₄-alkoxy, carboxyl and C₁ -C₄ -alkoxycarbonyl, and it being possible forthe phenyl ring additionally to carry a number of halogen atoms suchthat the total number of radicals is 4 or 5; thienylmethyl which mayfurthermore carry a halogen atom; R^(f) is C₁ -C₄ -alkyl which may bemonosubstituted by C₁ -C₄ -alkylthio or by C₁ -C₄ -alkoxy; a 5-memberedor 6-membered saturated or monounsaturated ring system which, inaddition to carbon members, may contain an oxygen or sulfur atom or asulfinyl or sulfonyl group, where this ring may carry up to three of thefollowing radicals: hydroxyl, halogen, C₁ -C₄ -alkyl, partially orcompletely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄-alkylthio; a 10-membered saturated or monounsaturated heterocyclicstructure which contains two oxygen atoms or sulfur atoms and may besubstituted by up to three C₁ -C₄ -alkyl groups and/or methoxy groups;phenyl or pyridyl, where these groups may, if desired, carry up to threeradicals selected from the group consisting of: C₁ -C₄ -alkyl, partiallyor completely halogenated C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₃ -C₆ -alkenyloxy, C₃ -C₆ -alkynyloxy, C₁ -C₄ -alkoxy-C₁-C₃ -alkyl, C₁ -C₄ -dialkoxy-C₁ -C₃ -alkyl, formyl, halogen andbenzoylamino; pyrrolyl, pyrazolyl, thiazolyl or isoxazolyl, each ofwhich may carry a C₁ -C₄ -alkyl group; R^(g) is hydrogen or hydroxyl or,when R^(f) is C₁ -C₆ -alkyl, is C₁ -C₆ -alkyl; R^(h) is hydrogen, cyano,halogen, C₁ -C₄ -alkoxycarbonyl or a group ##STR118## and R^(i) ishydrogen or one equivalent of an environmentally compatible cation.
 4. Aherbicidal composition as claimed in claim 3, containing a substituted5-aminopyrazole I' and a herbicide X or a herbicide XI in a weight ratioof from 0.01:1 to 10:1.
 5. A method for selectively controllingundesirable plant growth, wherein a substituted 5-aminopyrazole I' andA)a 2-(4-hetaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivative ofthe formula X or B) a cyclohexenone derivative of the formula XI asdefined in claim 3 are applied simultaneously or in succession, duringor after sowing of the crops or before or during emergence of the crops.6. A method for selectively controlling undesirable plant growth,wherein the leaves of the crops and of the undesirable plants aretreated simultaneously or in succession, by the postemergence method,with a substituted 5-aminopyrazole I' andA) with a 2-(4-hetaryloxy)- or2-(4-aryloxy)-phenoxyacetic acid derivative of the formula X or B) witha cyclohexenone derivative of the formula XI as defined in claim
 3. 7. Amethod for preventing damage to cropsA) by herbicidal 2-(4-hetaryloxy)-or 2-(4-aryloxy)-phenoxyacetic acid derivatives of the formula X or B)by herbicidal cyclohexenone derivatives of the formula XI as defined inclaim 3,wherein the seed of the crops is treated with an antagonisticamount of substituted 5-aminopyrazole of the formula I', where I'corresponds to the definition of I without the exception.
 8. A method asdefined in claim 5, wherein the crops are barley, wheat, corn, sorghumand rice.
 9. A process as defined in claim 6, wherein the crops arebarley, wheat, cron, sorghum and rice.
 10. A process as defined in claim7, wherein the crops are barley, wheat, corn, sorghum and rice.